EP3650238B1 - Method for marking workpieces - Google Patents

Method for marking workpieces Download PDF

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Publication number
EP3650238B1
EP3650238B1 EP18205412.2A EP18205412A EP3650238B1 EP 3650238 B1 EP3650238 B1 EP 3650238B1 EP 18205412 A EP18205412 A EP 18205412A EP 3650238 B1 EP3650238 B1 EP 3650238B1
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EP
European Patent Office
Prior art keywords
marking
ink
workpiece
fixing
radiation
Prior art date
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EP18205412.2A
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German (de)
French (fr)
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EP3650238A1 (en
Inventor
Thomas Härtling
Björn Erik Mai
Christoph Zeh
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Priority to ES18205412T priority Critical patent/ES2904878T3/en
Priority to EP18205412.2A priority patent/EP3650238B1/en
Publication of EP3650238A1 publication Critical patent/EP3650238A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0047—Digital printing on surfaces other than ordinary paper by ink-jet printing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0058—Digital printing on surfaces other than ordinary paper on metals and oxidised metal surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0072—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using mechanical wave energy, e.g. ultrasonics; using magnetic or electric fields, e.g. electric discharge, plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams

Definitions

  • a method for marking workpieces is given.
  • the pamphlets DE 10 2016 015 772 A1 and WO 2018/065228 A1 each relate to a method in which an ink containing ceramic pigments for a marking is applied to a workpiece before rolling. The marking is pressed into the workpiece during rolling or is melted, so that an intimate connection is created between the workpiece and the marking.
  • One problem to be solved is to provide a method with which a workpiece can be efficiently connected to a temperature-stable marking can be firmly and permanently connected.
  • a marking is applied to a workpiece with the method. With the marking, it is preferably possible to clearly identify the workpiece.
  • the marking is, for example, a lettering, a number, a label, a barcode or a matrix code, for example a data matrix code, DMC for short, or a QR code.
  • the marking is preferably machine-readable.
  • the method comprises the step of providing the at least one workpiece.
  • the workpiece can be a blank.
  • the blank is, for example, a sheet of metal and / or a piece of metal to be processed, such as a cast part.
  • the method comprises the step of applying at least one ink for a marking to the workpiece. It is possible that multicolored markings are to be produced and that accordingly several different inks can be used. Only exactly one ink is preferably used.
  • the ink is only applied locally.
  • the ink is only applied to the workpiece where the ink is actually needed for the marking. A subsequent removal of compared to the Workpiece colored material from the ink can thus be omitted.
  • the method comprises the step of fixing the ink to the marking.
  • the ink is preferably brought to a temperature of at least 400 ° C. or at least 500 ° C. or at least 600 ° C. for a short time.
  • this temperature can be a maximum of 1200 ° C or a maximum of 1000 ° C or a maximum of 950 ° C.
  • the ink can already be pre-dried when it is fixed, for example because a solvent has evaporated.
  • the workpiece is only heated locally in an area with the marking during fixing. Remaining areas of the workpiece are then not or not significantly affected by the temperature effect during fixing. Not significant means in particular that the workpiece does not change in terms of its mechanical, optical or functional properties in a process-relevant manner. If only local heating is generally used, for example for hot forming, then the area of the marking is also preferred warmed up. This means that there can then be several local temperature entries laterally and / or temporally.
  • a fixation process can take place in two steps: First, drying takes place, i.e. the removal of water and / or organic solvents. This step is typically done at room temperature. This is followed by firing and / or sintering for compression, solidification and / or for contrast enhancement and / or long-term fixation of the marking at high temperatures of, for example, at least 250 ° C or 400 ° C. As a result of this temperature effect, a substrate material of the workpiece and the ink pigments are materially bonded.
  • the in particular ceramic pigments and / or the adhesion promoter are preferably sintered preferably also based on a glass, a ceramic or a glass ceramic.
  • the entire component has been heated up to date, which leads to relatively high energy costs and stresses the component.
  • the fixing is usually carried out in an oven environment, which is either operated only for this purpose or which primarily serves a different purpose and can also carry out the fixing of the marking in parallel.
  • an oven is used for a main purpose other than to fix the marking, one is dependent on a position of the printer at or near the oven when printing the marking, or the marking must be so firmly attached to the component in the unfired state that the marking is not lost or damaged by handling the workpiece or by other work steps. This reduces the flexibility of the possible uses and / or prevents relevant areas of the process chain from being able to be recorded with the aid of the marking.
  • this local heating takes place by means of an electrical resistor, electrodes being attached to the workpiece.
  • the information of the marking which is carried by the inorganic adhesion promoter and the pigments in the form of a pre-structured marking and which is preferably applied by means of inkjet printing, is firmly connected to the workpiece or component in the method described here by local heating.
  • the method described and the marking produced with it can be used, for example, in the fields of application of direct part marking of metallic components, sheet metal forming, hot soldering and / or metal casting.
  • the ink additionally comprises an inorganic binder, which is preferably also contained in the finished marking.
  • the inorganic binder is preferably in the form of particles in the ink.
  • An average particle diameter of the particles of the binder in the ink is preferably at least 10 nm or at least 0.1 ⁇ m or at least 0.2 ⁇ m and / or at most 0.1 mm or at most 50 ⁇ m or at most 10 ⁇ m.
  • the ink contains ceramic pigments.
  • the ceramic pigments preferably give the marking and / or a contrast to the workpiece.
  • the term “ceramic pigments” includes glass ceramics which have amorphous and crystalline subregions. It is possible that such a glass ceramic is only formed through the fixing, such a glass ceramic then preferably consisting of the binding agent and the ceramic pigments.
  • an average particle diameter of the ceramic pigments in the ink and / or in the finished marking is at least 10 nm or at least 50 nm or at least 0.1 ⁇ m and / or at most 30 ⁇ m or at most 5 ⁇ m or at most 500 nm or at most 200 nm.
  • the term "mean diameter” preferably relates to a D50 value, that is to say to a median value. It is possible that the mean diameter of the ceramic pigments in the ink is larger or smaller than the mean diameter of the particles of the binder, for example by at least a factor of 2.
  • the marking has a reflectance difference and / or a reflectance difference and / or an albedo difference of at least 15 percentage points or 25 percentage points or 40 percentage points in relation to the workpiece at least in part of the near ultraviolet, the visible and / or the near infrared spectral range .
  • This difference is achieved, for example, on the basis of a color of the ceramic pigments and / or on the basis of a refractive index difference and / or a material-specific absorption difference and / or emissivity difference between the ceramic pigments in particular and the surroundings of the pigments.
  • the marking can be clearly distinguished from a surface of the workpiece, for example by a camera or by the human eye.
  • the marking has a high contrast to a surface of the workpiece, at least under suitable lighting conditions that can be used for reading out the marking.
  • the near ultraviolet spectral range is understood to mean, in particular, the range from 300 nm to 420 nm, the visible spectral range in particular denotes wavelengths from 420 nm to 760 nm and the near infrared spectral range denotes wavelengths from 760 nm to 1500 nm.
  • optical filters can be used which, for example, block an excitation wavelength of a phosphor, so that only the radiation generated by the phosphor due to the excitation is then detected.
  • the marking fulfills the requirements with regard to the contrast and / or a difference in brightness Current standard ISO / IEC 15415, which is required for directly marked components.
  • the ceramic pigments are made from Al 2 O 3 , TiO 2 and / or ZrO 2 .
  • the binder preferably comprises SiO 2 as the main component.
  • step C) the temperature of at least 400 ° C. is applied for at most 1 min or for at most 0.5 min or for at most 10 s or for at most 1 s. This means, in particular, that an energy source for reaching the relevant temperature in step C) is active on the ink and / or on the marking at most for the specified time period.
  • the workpiece is a metal sheet such as an iron sheet or a steel sheet.
  • a thickness of the metal sheet is, for example, at least 0.1 mm or 0.3 mm or 0.5 mm and / or at most 8 mm or 5 mm or 3 mm.
  • the metal sheet can have a constant thickness or also be varied in thickness.
  • the workpiece undergoes hot forming, for example pressing or deep drawing, for example punched, planar sheets at a deformation temperature.
  • the deformation temperature is preferably at least 700 ° C. or at least 800 ° C. or at least 880 ° C.
  • the deformation temperature is at most 1100 ° C or at most 1000 ° C or at most 950 ° C.
  • the marking is preferably fixed at a temperature below the deformation temperature, for example at least 200 ° C. below the deformation temperature.
  • the workpiece has a scaling protection layer.
  • the anti-scaling layer is designed to prevent or greatly slow down an oxidation of the metal sheet, in particular in the region of the deformation temperature in an oxygen-containing atmosphere.
  • the anti-scaling layer comprises or consists of aluminum, silicon, zinc and / or at least one metal oxide.
  • the anti-scaling layer is a layer produced by hot-dip galvanizing or a layer made of an aluminum-silicon alloy.
  • Protective layers made of or with metal oxides such as aluminum oxide can also be used.
  • the anti-scaling layer can also be a protective layer with particles on the nanometer scale, for example an x-tec coating from the manufacturer NANO-X GmbH.
  • a thickness of the anti-scaling layer is, for example, at least 100 nm or 250 nm or 1 ⁇ m and / or at most 30 ⁇ m or 10 ⁇ m or 2 ⁇ m.
  • a preferred composition of the anti-scaling layer is: 87% Al, 10% Si and 3% Fe. The preferred thickness of the anti-scaling layer is between 1 ⁇ m and 40 ⁇ m.
  • the marking is produced directly on the anti-scaling layer.
  • the ink can be printed on the anti-scaling layer.
  • the ink is applied directly to the metal sheet.
  • the marking is still readable, in particular machine-readable, even after step D). This means that the marking is not destroyed by the hot forming. However, it is possible, although not preferred, for the area with the marking to change its shape during the hot forming.
  • the fixing in step C) takes place by means of a radiation flash.
  • Radiation from the radiation flash is absorbed in the ink and / or on a workpiece surface. This applies the temperature for fixing.
  • the radiation flash can be short and last, for example, for a maximum of 1 s or 0.1 s or 0.01 s.
  • the radiation flash is preferably incoherent radiation, but alternatively coherent radiation, that is to say laser radiation, can also be used.
  • the radiation of the radiation flash is predominantly ultraviolet radiation.
  • a wavelength of maximum intensity of the radiation flash is in this case preferably between 250 nm and 370 nm inclusive.
  • infrared radiation can be used, in particular with a maximum intensity wavelength between 1 ⁇ m and 2 ⁇ m inclusive.
  • a component has been added to the ink that specifically absorbs the radiation. This component can also be realized by the ceramic pigments and / or by the inorganic binder.
  • the fixing in step C) takes place by means of induction.
  • the heating thus takes place inductively, in particular via alternating magnetic fields that can generate eddy currents locally in the area of the marking.
  • the heating is carried out without contact.
  • the ink in step B) comprises at least one organic binder.
  • the organic binder is, for example, an acrylate-based material.
  • the binder thus acts as a kind of adhesive for the ceramic pigments and the particles of the inorganic binder until it is fixed at high temperatures. After fixing, the organic binder is preferably no longer present or at least has no function.
  • the ink in step B) comprises at least one solvent, in particular water or an organic solvent such as an alcohol.
  • the ink can be dried by evaporating the solvent. For example, drying in this way makes the ink smudge-proof.
  • the ink can have a dispersant and / or a plasticizer.
  • the ink can also be designed as a paste, for example as in the publication DE 602 18 966 T2 described.
  • the dried ink is preferably composed of the organic binder, the ceramic pigments and the inorganic binder.
  • the finished marking preferably consists of the ceramic pigments and the inorganic binder, which can be fused or sintered to form a ceramic or a glass ceramic.
  • the ink consists of the solvent, the ceramic pigments and the inorganic binder and the dried ink and the fixed marking consist of the ceramic pigments and the inorganic binder. If the ink is free of an organic binder, the marking is less affected during fixing, for example by decomposition of the organic binder and / or by outgassing of components of the possibly decomposed organic binder, which can result in bubbles. In addition, inks without organic binders can be produced more cost-effectively.
  • a shape of the marking is already defined in step B). That is, in step C) there is no removal of material from the preferably dried ink or from the marking, with which an information content of the marking is changed. The information content of the marking is thus already complete immediately after step B).
  • the area with the marking, which is heated in step C) during fixing has at most three times the size of the marking itself. That is, the marking and the heated area are roughly the same size.
  • the area with the marking makes up at most 2% or at most 10% of the Workpiece.
  • the marking is therefore relatively small compared to the entire workpiece.
  • the marking is raised above a metal sheet of the workpiece at least in the area with the marking. That is, the marking can be a relief that rises from the workpiece.
  • the marking is planarized in a step E) after step C), preferably also after step D).
  • This planarization takes place, for example, by means of painting with a varnish.
  • a lacquer can be applied continuously over the marking.
  • the lacquer can be transparent to radiation used to read out the marking.
  • the lacquer is at least impermeable to visible light. If the marking is intended, for example, for reading in the infrared spectral range, then the lacquer can be permeable in the relevant spectral range.
  • the fixing to the marking C) takes place with a separate heating means. This means that the heat source for applying the increased temperature is only used for fixing and not also for other process steps when machining the workpiece.
  • the ink and the marking comprise at least one phosphor.
  • a contrast between the marking and the workpiece can be increased by the at least one phosphor.
  • the ceramic pigments consist of at least one ceramic or glass ceramic phosphor.
  • the luminescent material can be set up to shorten the wavelength of an excitation radiation, also referred to as upconversion, and, for example, convert infrared light into visible light.
  • the phosphor can convert short-wave light into long-wave light. It is possible that the phosphor is in its Luminescence properties is changed. In this way, a quality control can also be achieved as to whether the hot forming has taken place with the correct process parameters.
  • the luminescent material is a thermoluminescent material, that is to say a material that luminesces when a threshold temperature is reached.
  • the threshold temperature is preferably at least 125 ° C or 175 ° C.
  • the phosphor then preferably comprises one or more of the following elements as doping and / or as a component of a crystal lattice or a host lattice: Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb.
  • the thermoluminescent phosphor is particularly preferably NaYF 4 : Er, Yb. The use of such phosphors is for example in the document DE 10 2017 125 006 A1 described.
  • a workpiece is also specified.
  • the workpiece is marked with a method as specified in connection with one or more of the above-mentioned embodiments.
  • the workpiece produced according to the invention has the marking, the workpiece having a discoloration and / or a changed material structure only in the area of the marking, which is caused by heating to a temperature of at least 400 ° C. in step C).
  • the workpiece is preferably a hot-formed metal part or a metal blank which is provided for hot forming.
  • the minimum temperature for the Determine the fixation of the marking The local discoloration and / or changed material structure of the workpiece on the marking can be used to determine in which spatial area the temperature was applied to the workpiece for fixing, i.e. whether only local heating took place. For example, the local heating is extreme when the marking is fixed in a tarnishing color around the marking.
  • a metal sheet 11 with a workpiece surface 10 is provided.
  • the metal sheet 11 is preferably a steel sheet, for example a stamped but still flat sheet.
  • Figure 2 it is shown that an ink 20 for a marking 2 is printed on the workpiece surface 10.
  • the printing takes place with a printing nozzle 5.
  • the marking 2 can thus be produced in a structured manner by means of inkjet printing.
  • the marking 2 is in this case already produced essentially with its final shape.
  • the marking 2 is, for example, a lettering.
  • the still moist ink 20 can preferably dry at room temperature to give a dried ink 20 '.
  • the dried ink 20 ' preferably adheres to the workpiece surface 10 in a smudge-proof manner, but would disappear again in the event of greater friction or the influence of solvents.
  • the dried ink 20 ' is irradiated with ultraviolet radiation with the aid of an irradiation head 31.
  • the irradiation is concentrated on a small area 3 around the later, finished marking 2.
  • the dried ink 20 ' is strongly heated, for example to approximately 600.degree.
  • the ink 20 ′ is thereby fixed to the marking 2.
  • the irradiation can take place in an unstructured and contiguous manner over the entire marking 2.
  • the marking 2 is then not scanned with a laser beam, for example.
  • the irradiation takes place, for example, with UV radiation around 360 nm with an energy density of approximately 8 J / cm 2 .
  • the irradiation lasts, for example, only around 100 ⁇ s. In this way, thermal loads on the metal sheet 11 outside the area 3 with the marking 2 can be greatly reduced.
  • the radiation used is in particular incoherent radiation, for example from a flash lamp.
  • Figure 4 the finished, fixed marker 2 is shown. Due to the irradiation and the associated increase in temperature in the area 3, it is possible that a color change 6 occurs around the actual marking 2. The color change 6, however, is limited to a small area around the marking 2.
  • a hot forming of the workpiece 1 takes place.
  • the fixed marking 2 can be applied in areas of the workpiece 1 that are affected by the hot forming.
  • the marking 2 is located outside of areas in which hot forming takes place.
  • the legibility of the marking 2 is not impaired or only slightly impaired by the hot forming.
  • the marking 2 can therefore already be attached and cannot be lost with the component in an early manufacturing stage of the workpiece 1 and independently of other process steps. This enables efficient and reliable tracking of the workpiece, even across long process chains.
  • a coating 4 is applied to the workpiece surface 10 in areas or over the whole area.
  • the coating 4 is, for example, a lacquer. It is possible for the marking 2 to be hidden from the human eye by the coating 4, but the coating can optionally still be machine-readable.
  • the ink 20 is applied to the workpiece 1.
  • the ink 20 is composed of ceramic pigments 21, particles of an inorganic binder 22, an organic binder 23, a solvent 24 and a dispersing aid 25.
  • the dried ink 20 ′ is illustrated, which no longer contains any solvent 24.
  • the pigments 21 and the binder 22 as well as the optionally present dispersing aid 25 are held together by the organic binder 23 so that the dried ink 20 ′ is attached to the workpiece 1 in a smudge-proof manner.
  • the sintering and fixing to mark 2 has taken place.
  • the organic binder 23 and the dispersing aid are no longer present or only present in traces which no longer fulfill a specific function.
  • contiguous areas of the marking 2 are preferably formed for individual characters. Within a contiguous area, the marking 2 preferably shows a homogeneous color impression for an observer and / or for a camera.
  • the contiguous areas can be formed as smooth elevations over the workpiece.
  • the contiguous areas are preferably formed by a glass ceramic which is produced from the pigments 21 and the binder 22.
  • the ink 20, as in Figs Figures 7 to 9 can also be used in all other exemplary embodiments.
  • FIGS 10 and 11 are alternatives to the step of heating the Figure 2 shown.
  • contact needles 32 are placed on the electrically conductive workpiece 1, with more than two contact needles 32 being able to be used. Via the contact needles 32, electrical currents are generated in the workpiece 1 in the area 3, which lead to a strong local heating of the workpiece 1 and thus the dried ink 20 '. This enables the fixing to the marking 2 to be carried out.
  • eddy currents in particular can be used in the workpiece for fixing in a contactless manner via magnetic fields.
  • a heating tip 33 is brought close to the ink 20 or to the optionally dried ink 20 '.
  • the heating tip 33 is heated, whereby the ink 20 is dried and heated or the already dried ink 20 ′ is heated and fixed to the marking 2.
  • the heating tip 33 is preferably operated only over the dried ink 20 '.
  • the entire marking 2 is preferably completed in a single heating step with the heating tip 33.
  • Figure 10 illustrates that the marking 2 is formed by a bar code.
  • mark 2 is a matrix code.
  • Such types of markings 2 can correspondingly also be used in all other exemplary embodiments.
  • a separate heating means 31, 32, 33 is used in each case, which is used specifically only for fixing the dried ink 20 ′ or for drying and fixing the ink 20.
  • the fixation for the marking 2 according to the method not according to the invention of FIG Figures 12 to 14 combined with a further process step.
  • the workpiece 1 is provided with the dried ink 20 ', which is only indicated schematically.
  • the workpiece 1 is deformed with a deforming tool 34a, 34b.
  • the deforming tool 34b which covers the dried ink 20 ', is heated.
  • the resulting, hot-formed workpiece 1 with the finished marking 2 is shown in FIG Figure 14 shown.
  • the components shown in the figures preferably follow one another in the specified order. Layers that do not touch one another in the figures are preferably spaced apart from one another. As far as lines are drawn parallel to one another, the corresponding surfaces are preferably also aligned parallel to one another. Likewise, unless otherwise indicated, the relative positions of the components drawn are shown correctly in the figures.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Thermal Sciences (AREA)
  • Toxicology (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Description

Es wird ein Verfahren zur Markierung von Werkstücken angegeben.A method for marking workpieces is given.

Aus der Druckschrift EP 3 109 058 A2 ist ein Verfahren bekannt, bei dem mittels eines Lasers und mittels eines Leuchtstoffs eine Markierung an einem Werkstück angebracht wird.From the pamphlet EP 3 109 058 A2 a method is known in which a marking is applied to a workpiece by means of a laser and a fluorescent substance.

In der Druckschrift DE 10 2015 107 744 B3 findet sich ein Markierungsverfahren für Werkstücke, die warmumgeformt werden.In the pamphlet DE 10 2015 107 744 B3 there is a marking process for workpieces that are hot-formed.

Die Druckschriften DE 10 2016 015 772 A1 und WO 2018/065228 A1 betreffen jeweils ein Verfahren, bei dem eine keramische Pigmente enthaltende Tinte für eine Markierung auf ein Werkstück vor einem Walzen aufgebracht wird. Die Markierung wird beim Walzen in das Werkstück eingedrückt oder wird aufgeschmolzen, sodass eine innige Verbindung zwischen dem Werkstück und der Markierung entsteht.The pamphlets DE 10 2016 015 772 A1 and WO 2018/065228 A1 each relate to a method in which an ink containing ceramic pigments for a marking is applied to a workpiece before rolling. The marking is pressed into the workpiece during rolling or is melted, so that an intimate connection is created between the workpiece and the marking.

Ein Verfahren, bei dem keramische Partikel auf ein heißes Werkstück, zum Beispiel aus Stahl, geblasen werden und bei Berührung mit dem Werkstück mit diesem fest verbunden werden, sodass eine dauerhafte Markierung entsteht, wird in der Druckschrift DE 26 17 671 A1 angegeben.A process in which ceramic particles are blown onto a hot workpiece, for example made of steel, and are firmly connected to the workpiece when they come into contact with it, so that a permanent marking is created, is described in the publication DE 26 17 671 A1 specified.

Eine zu lösende Aufgabe besteht darin, ein Verfahren anzugeben, mit dem ein Werkstück effizient mit einer temperaturstabilen Markierung fest und dauerhaft verbunden werden kann.One problem to be solved is to provide a method with which a workpiece can be efficiently connected to a temperature-stable marking can be firmly and permanently connected.

Diese Aufgabe wird durch ein Verfahren mit den Merkmalen des Anspruchs 1 gelöst. Bevorzugte Weiterbildungen sind Gegenstand der abhängigen Ansprüche.This object is achieved by a method with the features of claim 1. Preferred developments are the subject of the dependent claims.

Erfindungsgemäß wird mit dem Verfahren an einem Werkstück eine Markierung angebracht. Mit der Markierung ist es bevorzugt möglich, das Werkstück eindeutig zu identifizieren. Die Markierung ist zum Beispiel ein Schriftzug, eine Nummer, eine Kennzeichnung, ein Strichcode oder ein Matrixcode, zum Beispiel ein Data Matrix Code, kurz DMC, oder ein QR-Code. Bevorzugt ist die Markierung maschinenlesbar.According to the invention, a marking is applied to a workpiece with the method. With the marking, it is preferably possible to clearly identify the workpiece. The marking is, for example, a lettering, a number, a label, a barcode or a matrix code, for example a data matrix code, DMC for short, or a QR code. The marking is preferably machine-readable.

Erfindungsgemäß umfasst das Verfahren den Schritt des Bereitstellens des mindestens einen Werkstücks. Bei dem Werkstück kann es sich dabei um einen Rohling handeln. Der Rohling ist zum Beispiel ein Metallblech und/oder ein weiterzuverarbeitendes Metallstück wie ein Gussteil.According to the invention, the method comprises the step of providing the at least one workpiece. The workpiece can be a blank. The blank is, for example, a sheet of metal and / or a piece of metal to be processed, such as a cast part.

Erfindungsgemäß umfasst das Verfahren den Schritt des Aufbringens zumindest einer Tinte für eine Markierung auf das Werkstück. Es ist möglich, dass mehrfarbige Markierungen erzeugt werden sollen und dass demgemäß mehrere verschiedene Tinten zum Einsatz kommen können. Bevorzugt wird nur genau eine Tinte verwendet.According to the invention, the method comprises the step of applying at least one ink for a marking to the workpiece. It is possible that multicolored markings are to be produced and that accordingly several different inks can be used. Only exactly one ink is preferably used.

Erfindungsgemäß wird die Tinte nur lokal aufgebracht. Insbesondere wird die Tinte nur dort auf dem Werkstück angebracht, wo die Tinte für die Markierung tatsächlich benötigt wird. Ein nachträgliches Entfernen von gegenüber dem Werkstück farbigem Material aus der Tinte kann somit unterbleiben.According to the invention, the ink is only applied locally. In particular, the ink is only applied to the workpiece where the ink is actually needed for the marking. A subsequent removal of compared to the Workpiece colored material from the ink can thus be omitted.

Erfindungsgemäß umfasst das Verfahren den Schritt des Fixierens der Tinte zu der Markierung. Beim Fixieren wird die Tinte bevorzugt kurzzeitig auf eine Temperatur von mindestens 400 °C oder mindestens 500 °C oder mindestens 600 °C gebracht. Zusätzlich kann diese Temperatur bei höchstens 1200 °C oder bei höchstens 1000 °C oder bei höchstens 950 °C liegen. Durch die Temperatureinwirkung werden die die Markierung bildenden Bestandteile der Tinte fest mit dem Werkstück verbunden.According to the invention, the method comprises the step of fixing the ink to the marking. When fixing, the ink is preferably brought to a temperature of at least 400 ° C. or at least 500 ° C. or at least 600 ° C. for a short time. In addition, this temperature can be a maximum of 1200 ° C or a maximum of 1000 ° C or a maximum of 950 ° C. As a result of the action of temperature, the components of the ink that form the marking are firmly bonded to the workpiece.

Es ist möglich, dass beim Fixieren nicht mehr alle Bestandteile der ursprünglich aufgebrachten Tinte vorhanden sind. So kann die Tinte beim Fixieren bereits vorgetrocknet sein, zum Beispiel indem ein Lösungsmittel abgedampft ist. Bei einem solchen optionalen Vortrocknen erfolgt besonders bevorzugt keine oder keine ausgeprägte Temperaturbehandlung. Das heißt, das Vortrocknen kann bei Temperaturen unterhalb von 150 °C oder unterhalb von 100 °C erfolgen, bevorzugt bei Raumtemperatur, also ungefähr 25 °C.It is possible that not all components of the originally applied ink are present when fixing. For example, the ink can already be pre-dried when it is fixed, for example because a solvent has evaporated. In the case of such an optional predrying, it is particularly preferable for no or no pronounced temperature treatment to take place. This means that the predrying can take place at temperatures below 150 ° C or below 100 ° C, preferably at room temperature, that is to say approximately 25 ° C.

Erfindungsgemäß wird das Werkstück beim Fixieren nur lokal in einem Bereich mit der Markierung erhitzt. Übrige Bereiche des Werkstücks sind dann von der Temperatureinwirkung beim Fixieren nicht oder nicht signifikant betroffen. Nicht signifikant bedeutet insbesondere, dass sich das Werkstück in seinen mechanischen oder optischen oder funktionalen Eigenschaften nicht prozessrelevant ändert. Falls generell nur lokal erhitzt wird, zum Beispiel für eine Warmumformung, dann wird bevorzugt auch der Bereich der Kennzeichnung erwärmt. Das heißt, es kann dann lateral und/oder zeitlich mehrere lokale Temperatureinträge geben.According to the invention, the workpiece is only heated locally in an area with the marking during fixing. Remaining areas of the workpiece are then not or not significantly affected by the temperature effect during fixing. Not significant means in particular that the workpiece does not change in terms of its mechanical, optical or functional properties in a process-relevant manner. If only local heating is generally used, for example for hot forming, then the area of the marking is also preferred warmed up. This means that there can then be several local temperature entries laterally and / or temporally.

Erfindungsgemäß dient das Verfahren zum Markieren von bevorzugt metallischen Werkstücken, die nachfolgend warmumgeformt werden können, und umfasst die folgenden Schritte:

  1. A) Bereitstellen des mindestens einen Werkstücks,
  2. B) lokales Aufbringen einer Tinte für eine Markierung (2) auf das Werkstück,
  3. C) Fixieren der Tinte zu der Markierung, wobei das Werkstück lokal, insbesondere nur lokal, in einem Bereich mit der Markierung erhitzt wird und beim Fixieren an der Tinte eine Temperatur von mindestens 400 °C appliziert wird.
According to the invention, the method is used to mark preferably metallic workpieces that can subsequently be hot-formed, and comprises the following steps:
  1. A) providing the at least one workpiece,
  2. B) local application of an ink for a marking (2) on the workpiece,
  3. C) fixing the ink to the marking, the workpiece being heated locally, in particular only locally, in an area with the marking and a temperature of at least 400 ° C. being applied to the ink during fixing.

Mit dem hier beschriebenen Verfahren ist es möglich, eine bevorzugt dauerhafte Beschriftung und/oder Bedruckung von Produkten und Objekten, unter anderem zu deren Kennzeichnung, vorzunehmen.With the method described here it is possible to carry out a preferably permanent labeling and / or printing of products and objects, among other things for their identification.

Bei der Aufbringung von pigmentierten Tinten kann ein Fixierungsprozess in zwei Schritten erfolgen: Zuerst erfolgt ein Trocknen, das heißt, das Entfernen von Wasser und/oder von organischen Lösungsmitteln. Dieser Schritt erfolgt typischerweise bei Raumtemperatur. Danach erfolgt ein Brennen und/oder Sintern zur Verdichtung, zur Verfestigung und/oder zur Kontrastverstärkung und/oder langfristigen Fixierung der Kennzeichnung bei hohen Temperaturen von beispielsweise mindestens 250 °C oder 400 °C. Durch diese Temperatureinwirkung werden ein Substratmaterial des Werkstücks und Tintenpigmente stoffschlüssig verbunden. Außerdem erfolgt bevorzugt die Versinterung der insbesondere keramischen Pigmente und/oder des Haftvermittlers, der bevorzugt ebenfalls auf einem Glas, einer Keramik oder einer Glaskeramik basiert.When applying pigmented inks, a fixation process can take place in two steps: First, drying takes place, i.e. the removal of water and / or organic solvents. This step is typically done at room temperature. This is followed by firing and / or sintering for compression, solidification and / or for contrast enhancement and / or long-term fixation of the marking at high temperatures of, for example, at least 250 ° C or 400 ° C. As a result of this temperature effect, a substrate material of the workpiece and the ink pigments are materially bonded. In addition, the in particular ceramic pigments and / or the adhesion promoter are preferably sintered preferably also based on a glass, a ceramic or a glass ceramic.

Insbesondere in der Metallverarbeitung wird dafür bisher das gesamte Bauteil erwärmt, was zu relativ hohen Energiekosten führt und das Bauteil belastet. Dazu wird das Fixieren meist in einer Ofenumgebung durchgeführt, die entweder nur dafür betrieben wird oder die primär einem anderen Zweck dient und die Fixierung der Markierung parallel mit durchführen kann.In metal processing in particular, the entire component has been heated up to date, which leads to relatively high energy costs and stresses the component. For this purpose, the fixing is usually carried out in an oven environment, which is either operated only for this purpose or which primarily serves a different purpose and can also carry out the fixing of the marking in parallel.

Wird ein Ofen für einen anderen Hauptzweck als zum Fixieren der Markierung verwendet, so ist man bei der Bedruckung der Markierung auf eine Position des Druckers am oder nahe am Ofen angewiesen oder die Markierung muss bereits im ungebrannten Zustand so fest mit dem Bauteil verbunden sein, dass die Markierung nicht durch eine Handhabung des Werkstücks und durch andere Arbeitsschritte verloren geht oder beschädigt wird. Dies vermindert die Flexibilität der Einsatzmöglichkeiten und/oder verhindert, dass relevante Bereiche der Prozesskette mit Hilfe der Markierung erfasst werden können.If an oven is used for a main purpose other than to fix the marking, one is dependent on a position of the printer at or near the oven when printing the marking, or the marking must be so firmly attached to the component in the unfired state that the marking is not lost or damaged by handling the workpiece or by other work steps. This reduces the flexibility of the possible uses and / or prevents relevant areas of the process chain from being able to be recorded with the aid of the marking.

Bei dem hier beschriebenen Verfahren erfolgt dagegen nur eine lokale Erhitzung des zum Beispiel bedruckten Areals für die Markierung zur Versinterung von Pigmenten und/oder des Haftvermittlers.In the method described here, on the other hand, there is only local heating of the, for example, printed area for the marking for sintering pigments and / or the adhesion promoter.

Dieses lokale Erhitzen erfolgt gemäß einer ersten erfindungsgemäßen Ausführungsform mittels eines elektrischen Widerstandes, wobei Elektroden am Werkstück angebracht werden.According to a first embodiment of the invention, this local heating takes place by means of an electrical resistor, electrodes being attached to the workpiece.

Die Informationen der Markierung, die vom anorganischen Haftvermittler und den Pigmenten in Form einer vorstrukturierten Kennzeichnung getragen wird und die bevorzugt mittels Tintenstrahldruck aufgebracht wird, wird bei dem hier beschriebenen Verfahren also durch lokales Erhitzen fest mit dem Werkstück oder Bauteil verbunden.The information of the marking, which is carried by the inorganic adhesion promoter and the pigments in the form of a pre-structured marking and which is preferably applied by means of inkjet printing, is firmly connected to the workpiece or component in the method described here by local heating.

Mit dem hier beschriebenen Verfahren ist insbesondere eine unmittelbare Fixierung der Markierung und damit Aufbringung entlang der gesamten Prozesskette, die das Werkstück zu durchlaufen hat, möglich. Im Vergleich zum Betrieb eines separaten Ofens sind Energieeinsparungen und Kosteneinsparung möglich. Ferner wird das Werkstück geschont. Es kann eine einfachere, damit besser verarbeitbare und kostengünstigere Tinte verwendet werden, da auf organische Binder insbesondere in der fertigen Markierung verzichtet werden kann. Weiterhin ist eine verbesserte Integration der Markierung in Metallverarbeitungsprozessen erreichbar.With the method described here, in particular, direct fixing of the marking and thus application along the entire process chain that the workpiece has to run through is possible. Energy and cost savings are possible compared to operating a separate furnace. The workpiece is also protected. A simpler ink that is easier to process and cheaper can be used, since organic binders, in particular in the finished marking, can be dispensed with. Furthermore, an improved integration of the marking in metalworking processes can be achieved.

Das beschriebene Verfahren und die damit erzeugte Markierung können zum Beispiel in den Anwendungsfeldern des Direct part marking von metallischen Bauteilen, der Blechumformung, beim Heißlöten und/oder im Metallguss herangezogen werden.The method described and the marking produced with it can be used, for example, in the fields of application of direct part marking of metallic components, sheet metal forming, hot soldering and / or metal casting.

Gemäß zumindest einer Ausführungsform umfasst die Tinte zusätzlich ein anorganisches Bindemittel, das bevorzugt auch in der fertigen Markierung enthalten ist. In der Tinte liegt das anorganische Bindemittel bevorzugt in Form von Partikeln vor. Ein mittlerer Teilchendurchmesser der Partikel des Bindemittels in der Tinte liegt bevorzugt bei mindestens 10 nm oder mindestens 0,1 µm oder mindestens 0,2 µm und/oder bei höchstens 0,1 mm oder höchstens 50 µm oder höchstens 10 µm.According to at least one embodiment, the ink additionally comprises an inorganic binder, which is preferably also contained in the finished marking. The inorganic binder is preferably in the form of particles in the ink. An average particle diameter of the particles of the binder in the ink is preferably at least 10 nm or at least 0.1 μm or at least 0.2 μm and / or at most 0.1 mm or at most 50 μm or at most 10 μm.

Gemäß zumindest einer Ausführungsform enthält die Tinte keramische Pigmente. Bevorzugt ist durch die keramischen Pigmente eine Farbgebung und/oder einen Kontrast der Markierung gegenüber dem Werkstück gegeben. Der Begriff "keramische Pigmente" schließt dabei Glaskeramiken, die amorphe und kristallene Teilgebiete aufweisen, mit ein. Es ist möglich, dass sich eine solche Glaskeramik erst durch das Fixieren bildet, wobei eine solche Glaskeramik dann bevorzugt aus dem Bindemittel und aus den keramischen Pigmenten besteht.According to at least one embodiment, the ink contains ceramic pigments. The ceramic pigments preferably give the marking and / or a contrast to the workpiece. The term “ceramic pigments” includes glass ceramics which have amorphous and crystalline subregions. It is possible that such a glass ceramic is only formed through the fixing, such a glass ceramic then preferably consisting of the binding agent and the ceramic pigments.

Beispielsweise sind die keramischen Pigmente und/oder die fertige Markierung aus einem oder aus mehreren der folgenden Materialien: Oxide wie BeO, MgO, Al2O3, SiO2, CaO, TiO2, Cr2O3, MnO, Fe2O3, ZnO, SrO, Y2O3, BaO, CeO2, UO2; Carbide wie Be2C, Be4C, Al4C3, SiC, TiC, Cr3C2, Mn3C, Fe3C, SrC2, YC2, ZrC, NbC, Mo2C, BaC2, CeC2, HfC, TaC, WC, UC; Nitride wie Be3N2, BN, Mg3N2, AlN, Si3N4, Ca3N2, TiN, VN, CrN, Mn3N2, Sr3N2, ZrN, NbN, Mo3N2, HfN, TaN, WN2, UN; Boride wie AlB4, CaB6, TiB2, VB2, CrB2, MnB, FeB, CoB, NiB, SrB6, YB6, ZrB2, NbB2, MoB2, BaB6, LaB6, CoB6, HfB2, TaB2, WB; Silicide wie CaSi, Ti5Si3, V5Si3, CrSi2, FeSi, CoSi, ZrSi2, NbSi2, MoSi2, TaSi2, WSi2. Auch oxidische Gläser, wie silikatische oder Boratgläser, sowie Multiphasenmaterialien, wie Al6Si2O13, oder gemischte Kristalle wie aus dem System Al2O3-Cr2O3, MgSiO4, CaSiO4, ZrSiO4, MgAl2O4, CaZrO3, SiAlON, AlON und/oder B4C-TiB2 können verwendet werden. Es ist auch möglich, keramische Pigmente mit einer nichtstöchiometrischen Zusammensetzung zu verwenden. Beispielsweise werden eines oder mehrere der folgenden Materialien für die keramischen Pigmente verwendet, allein oder in Kombination:

  • lila Pigmente wie BaCuSi2O6, Kobalt-Orthophosphate wie NH4MnP2O7,
  • blaue Pigmente wie schwefelhaltiges Sodiosilikat Na8-10Al6Si6O24S2-4, (Na,Ca)8(AlSiO4)6(S,SO4,Cl)1-2, Kobalt(II)stannat, CaCuSi4O10, BaCuSi4O10, Cu3(CO3)2(OH)2, Fe7(CN)18, YIn1-xMnxO3,
  • grüne Pigmente wie CdS in Kombination mit Cr2O3, (Cr2O3·H2O), CoZnO2, Cu2CO3(OH)2, CuHAsO3 oder K[(Al, FeIII), (FeII, Mg)] (AlSi3, Si4)O10(OH)2,
  • Gelbpigmente wie As2S3, BiVO4, PbCrO4, K3Co(NO2)6, Fe2O3·H2O, PbSnO4, Pb(Sn,Si)O3, SnS2, Cadmiumsulfoselenid, PbCrO4 + PbO,
  • rote Pigmente wie As4S4, Cd2SSe, Pb3O4, HgS,
  • schwarze Pigmente wie Fe3O4, MnO2, Ti2O3.
For example, the ceramic pigments and / or the finished marking are made of one or more of the following materials: Oxides such as BeO, MgO, Al 2 O 3 , SiO 2 , CaO, TiO 2 , Cr 2 O 3 , MnO, Fe 2 O 3 , ZnO, SrO, Y 2 O 3 , BaO, CeO 2 , UO 2 ; Carbides such as Be 2 C, Be 4 C, Al 4 C 3 , SiC, TiC, Cr 3 C 2 , Mn 3 C, Fe 3 C, SrC 2 , YC 2 , ZrC, NbC, Mo 2 C, BaC 2 , CeC 2 , HfC, TaC, WC, UC; Nitrides such as Be 3 N 2 , BN, Mg 3 N 2 , AlN, Si 3 N 4 , Ca 3 N 2 , TiN, VN, CrN, Mn 3 N 2 , Sr 3 N 2 , ZrN, NbN, Mo 3 N 2 , HfN, TaN, WN 2 , UN; Borides such as AlB 4 , CaB 6 , TiB 2 , VB2, CrB 2 , MnB, FeB, CoB, NiB, SrB 6 , YB 6 , ZrB 2 , NbB 2 , MoB 2 , BaB 6 , LaB 6 , CoB 6 , HfB 2 , TaB 2 , WB; Silicides such as CaSi, Ti5Si3, V 5 Si 3 , CrSi 2 , FeSi, CoSi, ZrSi 2 , NbSi 2 , MoSi 2 , TaSi 2 , WSi 2 . Oxidic glasses such as silicate or borate glasses, as well as multiphase materials such as Al 6 Si 2 O 13 , or mixed crystals such as those from the system Al 2 O 3 -Cr 2 O 3 , MgSiO 4 , CaSiO 4 , ZrSiO 4 , MgAl 2 O 4 , CaZrO 3 , SiAlON, AlON and / or B 4 C-TiB 2 can be used. It is also possible to use ceramic pigments with a non-stoichiometric composition. For example, one or more of the following materials are used for the ceramic pigments, alone or in combination:
  • purple pigments such as BaCuSi 2 O 6 , cobalt orthophosphates such as NH 4 MnP 2 O 7 ,
  • blue pigments such as sulphurous sodiosilicate Na 8 - 10 Al 6 Si 6 O 24 S 2-4 , (Na, Ca) 8 (AlSiO 4 ) 6 (S, SO 4 , Cl) 1-2 , cobalt (II) stannate, CaCuSi 4 O 10 , BaCuSi 4 O 10 , Cu 3 (CO 3 ) 2 (OH) 2 , Fe 7 (CN) 18 , YIn 1 - x Mn x O 3 ,
  • green pigments such as CdS in combination with Cr 2 O 3 , (Cr 2 O 3 · H 2 O), CoZnO 2 , Cu 2 CO 3 (OH) 2 , CuHAsO 3 or K [(Al, FeIII), (FeII, Mg )] (AlSi 3 , Si 4 ) O 10 (OH) 2 ,
  • Yellow pigments such as As 2 S 3 , BiVO 4 , PbCrO 4 , K 3 Co (NO 2 ) 6 , Fe 2 O 3 · H 2 O, PbSnO 4 , Pb (Sn, Si) O 3 , SnS 2 , cadmium sulfoselenide, PbCrO 4 + PbO,
  • red pigments like As 4 S 4 , Cd 2 SSe, Pb 3 O 4 , HgS,
  • black pigments such as Fe 3 O 4 , MnO 2 , Ti 2 O 3 .

Gemäß zumindest einer Ausführungsform beträgt ein mittlerer Partikeldurchmesser der keramischen Pigmente in der Tinte und/oder in der fertigen Markierung mindestens 10 nm oder mindestens 50 nm oder mindestens 0,1 µm und/oder höchstens 30 µm oder höchstens 5 µm oder höchstens 500 nm oder höchstens 200 nm. Der Begriff "mittlerer Durchmesser" bezieht sich vorzugsweise auf einen D50-Wert, also auf einen Medianwert. Es ist möglich, dass in der Tinte der mittlere Durchmesser der keramischen Pigmente größer oder kleiner ist als der mittlere Durchmesser der Partikel des Bindemittels, beispielsweise um mindestens einen Faktor von 2.According to at least one embodiment, an average particle diameter of the ceramic pigments in the ink and / or in the finished marking is at least 10 nm or at least 50 nm or at least 0.1 μm and / or at most 30 μm or at most 5 μm or at most 500 nm or at most 200 nm. The term "mean diameter" preferably relates to a D50 value, that is to say to a median value. It is possible that the mean diameter of the ceramic pigments in the ink is larger or smaller than the mean diameter of the particles of the binder, for example by at least a factor of 2.

Gemäß zumindest einer Ausführungsform weist die Markierung zumindest in einem Teil des nahen ultravioletten, des sichtbaren und/oder des nahinfraroten Spektralbereichs sowohl gegenüber dem Werkstück einen Reflexionsgradunterschied und/oder einen Remissionsgradunterschied und/oder einen Albedounterschied von mindestens 15 Prozentpunkten oder 25 Prozentpunkten oder 40 Prozentpunkten auf. Dieser Unterschied wird zum Beispiel aufgrund einer Farbe der keramischen Pigmente und/oder aufgrund eines Brechungsindexunterschieds und/oder eines materialspezifischen Absorptionsunterschieds und/oder Emissionsgradunterschiedes der insbesondere keramischen Pigmente zu einer Umgebung der Pigmente erzielt.According to at least one embodiment, the marking has a reflectance difference and / or a reflectance difference and / or an albedo difference of at least 15 percentage points or 25 percentage points or 40 percentage points in relation to the workpiece at least in part of the near ultraviolet, the visible and / or the near infrared spectral range . This difference is achieved, for example, on the basis of a color of the ceramic pigments and / or on the basis of a refractive index difference and / or a material-specific absorption difference and / or emissivity difference between the ceramic pigments in particular and the surroundings of the pigments.

Mit anderen Worten ist die Markierung aufgrund ihrer optischen Eigenschaften von einer Oberfläche des Werkstücks deutlich unterscheidbar, beispielsweise durch eine Kamera oder durch das menschliche Auge. Anders ausgedrückt weist die Markierung zu einer Oberfläche des Werkstücks einen hohen Kontrast auf, zumindest unter geeigneten Beleuchtungsbedingungen, die zum Auslesen der Markierung verwendet werden können. Unter dem nahen ultravioletten Spektralbereich wird insbesondere der Bereich von 300 nm bis 420 nm verstanden, der sichtbare Spektralbereich bezeichnet insbesondere Wellenlängen von 420 nm bis 760 nm und der nahinfrarote Spektralbereich Wellenlängen von 760 nm bis 1500 nm.In other words, because of its optical properties, the marking can be clearly distinguished from a surface of the workpiece, for example by a camera or by the human eye. In other words, the marking has a high contrast to a surface of the workpiece, at least under suitable lighting conditions that can be used for reading out the marking. The near ultraviolet spectral range is understood to mean, in particular, the range from 300 nm to 420 nm, the visible spectral range in particular denotes wavelengths from 420 nm to 760 nm and the near infrared spectral range denotes wavelengths from 760 nm to 1500 nm.

Zum Auslesen der Markierung können optische Filter verwendet werden, die zum Beispiel eine Anregungswellenlänge eines Leuchtstoffs blockieren, sodass dann nur die vom Leuchtstoff aufgrund der Anregung erzeugte Strahlung detektiert wird. Insbesondere erfüllt die Markierung hinsichtlich des Kontrasts und/oder eines Helligkeitsunterschieds die derzeitige Norm ISO / IEC 15415, welche für direkt markierte Bauteile gefordert wird.To read out the marking, optical filters can be used which, for example, block an excitation wavelength of a phosphor, so that only the radiation generated by the phosphor due to the excitation is then detected. In particular, the marking fulfills the requirements with regard to the contrast and / or a difference in brightness Current standard ISO / IEC 15415, which is required for directly marked components.

Gemäß zumindest einer Ausführungsform sind die keramischen Pigmente aus Al2O3, TiO2 und/oder ZrO2. Das Bindemittel umfasst als Hauptbestandteil bevorzugt SiO2.According to at least one embodiment, the ceramic pigments are made from Al 2 O 3 , TiO 2 and / or ZrO 2 . The binder preferably comprises SiO 2 as the main component.

Gemäß zumindest einer Ausführungsform wird im Schritt C) die Temperatur von mindestens 400 °C für höchstens 1 min oder für höchstens 0,5 min oder für höchstens 10 s oder für höchstens 1 s appliziert. Dies bedeutet insbesondere, dass eine Energiequelle zum Erreichen der betreffenden Temperatur im Schritt C) höchstens für die genannte Zeitspanne an der Tinte und/oder an der Markierung aktiv ist.According to at least one embodiment, in step C) the temperature of at least 400 ° C. is applied for at most 1 min or for at most 0.5 min or for at most 10 s or for at most 1 s. This means, in particular, that an energy source for reaching the relevant temperature in step C) is active on the ink and / or on the marking at most for the specified time period.

Gemäß zumindest einer Ausführungsform ist das Werkstück ein Metallblech wie ein Eisenblech oder ein Stahlblech. Eine Dicke des Metallblechs liegt beispielsweise bei mindestens 0,1 mm oder 0,3 mm oder 0,5 mm und/oder bei höchstens 8 mm oder 5 mm oder 3 mm. Das Metallblech kann eine gleichbleibende Dicke aufweisen oder auch dickenvariiert sein.According to at least one embodiment, the workpiece is a metal sheet such as an iron sheet or a steel sheet. A thickness of the metal sheet is, for example, at least 0.1 mm or 0.3 mm or 0.5 mm and / or at most 8 mm or 5 mm or 3 mm. The metal sheet can have a constant thickness or also be varied in thickness.

Gemäß zumindest einer Ausführungsform durchläuft das Werkstück nach dem Schritt C) in einem Schritt D) eine Warmumformung, zum Beispiel ein Pressen oder ein Tiefziehen beispielsweise gestanzter, planarer Bleche bei einer Verformtemperatur. Insbesondere bei Stahlblechen oder bei Eisenblechen liegt die Verformtemperatur bevorzugt bei mindestens 700 °C oder mindestens 800 °C oder mindestens 880 °C. Alternativ oder zusätzlich liegt die Verformtemperatur bei höchstens 1100 °C oder höchstens 1000 °C oder höchstens 950 °C. Insbesondere liegt die Verformtemperatur bei ungefähr 920 °C. Das Fixieren der Markierung erfolgt bevorzugt bei einer Temperatur unterhalb der Verformtemperatur, zum Beispiel bei mindestens 200 °C unterhalb der Verformtemperatur.According to at least one embodiment, after step C), in a step D), the workpiece undergoes hot forming, for example pressing or deep drawing, for example punched, planar sheets at a deformation temperature. In the case of steel sheets or iron sheets in particular, the deformation temperature is preferably at least 700 ° C. or at least 800 ° C. or at least 880 ° C. Alternatively or additionally, the deformation temperature is at most 1100 ° C or at most 1000 ° C or at most 950 ° C. In particular, the Deformation temperature around 920 ° C. The marking is preferably fixed at a temperature below the deformation temperature, for example at least 200 ° C. below the deformation temperature.

Gemäß zumindest einer Ausführungsform weist das Werkstück eine Verzunderungsschutzschicht auf. Die Verzunderungsschutzschicht ist dazu eingerichtet, eine Oxidation des Metallblechs insbesondere im Bereich der Verformtemperatur in einer sauerstoffhaltigen Atmosphäre zu verhindern oder stark zu verlangsamen.According to at least one embodiment, the workpiece has a scaling protection layer. The anti-scaling layer is designed to prevent or greatly slow down an oxidation of the metal sheet, in particular in the region of the deformation temperature in an oxygen-containing atmosphere.

Gemäß zumindest einer Ausführungsform umfasst die Verzunderungsschutzschicht Aluminium, Silizium, Zink und/oder mindestens ein Metalloxid oder besteht hieraus. Beispielsweise handelt es sich bei der Verzunderungsschutzschicht um eine über Feuerverzinkung hergestellte Schicht oder um eine Schicht aus einer Aluminium-Silizium-Legierung. Auch Schutzschichten aus oder mit Metalloxiden wie Aluminiumoxid können zum Einsatz kommen. Ebenso kann es sich bei der Verzunderungsschutzschicht um eine Schutzschicht mit Partikeln auf der Nanometerskala handeln, beispielsweise um eine x-tec-Beschichtung des Herstellers NANO-X GmbH. Eine Dicke der Verzunderungsschutzschicht liegt beispielsweise bei mindestens 100 nm oder 250 nm oder 1 µm und/oder bei höchstens 30 µm oder 10 µm oder 2 µm. Eine bevorzugte Zusammensetzung der Verzunderungsschutzschicht lautet: 87 % Al, 10 % Si und 3 % Fe. Die bevorzugte Dicke der Verzunderungsschutzschicht liegt zwischen 1 µm und 40 µm.According to at least one embodiment, the anti-scaling layer comprises or consists of aluminum, silicon, zinc and / or at least one metal oxide. For example, the anti-scaling layer is a layer produced by hot-dip galvanizing or a layer made of an aluminum-silicon alloy. Protective layers made of or with metal oxides such as aluminum oxide can also be used. The anti-scaling layer can also be a protective layer with particles on the nanometer scale, for example an x-tec coating from the manufacturer NANO-X GmbH. A thickness of the anti-scaling layer is, for example, at least 100 nm or 250 nm or 1 μm and / or at most 30 μm or 10 μm or 2 μm. A preferred composition of the anti-scaling layer is: 87% Al, 10% Si and 3% Fe. The preferred thickness of the anti-scaling layer is between 1 µm and 40 µm.

Gemäß zumindest einer Ausführungsform wird die Markierung unmittelbar auf der Verzunderungsschutzschicht erzeugt. Das heißt, die Tinte kann auf der Verzunderungsschutzschicht aufgedruckt werden. Alternativ erfolgt das Aufbringen der Tinte unmittelbar auf das Metallblech.According to at least one embodiment, the marking is produced directly on the anti-scaling layer. The that is, the ink can be printed on the anti-scaling layer. Alternatively, the ink is applied directly to the metal sheet.

Gemäß zumindest einer Ausführungsform ist die Markierung auch nach dem Schritt D) noch lesbar, insbesondere maschinenlesbar. Das heißt, durch das Warmumformen wir die Markierung nicht zerstört. Jedoch ist es möglich, wenngleich nicht bevorzugt, dass der Bereich mit der Markierung seine Form bei der Warmumformung ändert.According to at least one embodiment, the marking is still readable, in particular machine-readable, even after step D). This means that the marking is not destroyed by the hot forming. However, it is possible, although not preferred, for the area with the marking to change its shape during the hot forming.

Gemäß einer zweiten erfindungsgemäßen Ausführungsform erfolgt das Fixieren im Schritt C) durch einen Strahlungsblitz. Dabei wird Strahlung des Strahlungsblitzes in der Tinte und/oder an einer Werkstückoberfläche absorbiert. Hierdurch wird die Temperatur zum Fixieren appliziert. Der Strahlungsblitz kann kurz sein und zum Beispiel für höchstens 1 s oder 0,1 s oder 0,01 s andauern. Bei dem Strahlungsblitz handelt es sich bevorzugt um inkohärente Strahlung, alternativ kann aber auch kohärente Strahlung, also Laserstrahlung, zum Einsatz kommen.According to a second embodiment according to the invention, the fixing in step C) takes place by means of a radiation flash. Radiation from the radiation flash is absorbed in the ink and / or on a workpiece surface. This applies the temperature for fixing. The radiation flash can be short and last, for example, for a maximum of 1 s or 0.1 s or 0.01 s. The radiation flash is preferably incoherent radiation, but alternatively coherent radiation, that is to say laser radiation, can also be used.

Gemäß zumindest einer Ausführungsform ist die Strahlung des Strahlungsblitzes überwiegend ultraviolette Strahlung. Eine Wellenlänge maximaler Intensität des Strahlungsblitzes liegt in diesem Fall bevorzugt zwischen einschließlich 250 nm und 370 nm. Alternativ kann infrarote Strahlung herangezogen werden, insbesondere mit einer Wellenlänge maximaler Intensität zwischen einschließlich 1 µm und 2 µm. Es ist möglich, dass der Tinte ein Bestandteil beigegeben ist, der die Strahlung gezielt absorbiert. Dieser Bestandteil kann auch durch die keramischen Pigmente und/oder durch das anorganische Bindemittel verwirklicht sein.According to at least one embodiment, the radiation of the radiation flash is predominantly ultraviolet radiation. A wavelength of maximum intensity of the radiation flash is in this case preferably between 250 nm and 370 nm inclusive. Alternatively, infrared radiation can be used, in particular with a maximum intensity wavelength between 1 μm and 2 μm inclusive. It is possible that a component has been added to the ink that specifically absorbs the radiation. This component can also be realized by the ceramic pigments and / or by the inorganic binder.

Gemäß einer dritten erfindungsgemäßen Ausführungsform erfolgt das Fixieren im Schritt C) mittels Induktion. Somit erfolgt das Heizen induktiv, insbesondere über magnetische Wechselfelder, die lokal im Bereich der Markierung Wirbelströme generieren können. Das Heizen wird berührungslos durchgeführt.According to a third embodiment according to the invention, the fixing in step C) takes place by means of induction. The heating thus takes place inductively, in particular via alternating magnetic fields that can generate eddy currents locally in the area of the marking. The heating is carried out without contact.

Gemäß zumindest einer Ausführungsform umfasst die Tinte im Schritt B) zumindest einen organischen Binder. Mit diesem Binder ist erreichbar, dass die Tinte bereits vor dem Schritt C) wischfest an dem Werkstück angebracht ist. Der organische Binder ist zum Beispiel ein Material auf Acrylatbasis. Der Binder wirkt also für die keramischen Pigmente und die Partikel des anorganischen Bindemittels als eine Art Klebstoff, bis das Fixieren bei hohen Temperaturen erfolgt. Nach dem Fixieren ist der organische Binder bevorzugt nicht mehr vorhanden oder zumindest funktionslos.According to at least one embodiment, the ink in step B) comprises at least one organic binder. With this binder it can be achieved that the ink is already attached to the workpiece in a smudge-proof manner before step C). The organic binder is, for example, an acrylate-based material. The binder thus acts as a kind of adhesive for the ceramic pigments and the particles of the inorganic binder until it is fixed at high temperatures. After fixing, the organic binder is preferably no longer present or at least has no function.

Gemäß zumindest einer Ausführungsform umfasst die Tinte im Schritt B) zumindest ein Lösungsmittel, insbesondere Wasser oder ein organisches Lösungsmittel wie ein Alkohol. Durch ein Abdampfen des Lösungsmittels kann die Tinte getrocknet werden. Beispielsweise wird durch ein solches Trocknen erreicht, dass die Tinte wischfest wird.According to at least one embodiment, the ink in step B) comprises at least one solvent, in particular water or an organic solvent such as an alcohol. The ink can be dried by evaporating the solvent. For example, drying in this way makes the ink smudge-proof.

Zudem kann die Tinte ein Dispergiermittel und/oder einen Weichmacher aufweisen. Die Tinte kann auch als Paste gestaltet sein, etwa wie in der Druckschrift DE 602 18 966 T2 beschrieben.In addition, the ink can have a dispersant and / or a plasticizer. The ink can also be designed as a paste, for example as in the publication DE 602 18 966 T2 described.

Die getrocknete Tinte besteht bevorzugt aus dem organischen Binder, den keramischen Pigmenten und dem anorganischen Bindemittel. Die fertige Markierung besteht bevorzugt aus den keramischen Pigmenten und dem anorganischen Bindemittel, wobei diese zu einer Keramik oder zu einer Glaskeramik verschmolzen oder gesintert sein können.The dried ink is preferably composed of the organic binder, the ceramic pigments and the inorganic binder. The finished marking preferably consists of the ceramic pigments and the inorganic binder, which can be fused or sintered to form a ceramic or a glass ceramic.

Gemäß zumindest einer Ausführungsform besteht die Tinte aus dem Lösungsmittel, den keramischen Pigmenten und dem anorganischen Bindemittel und die getrocknete Tinte sowie die fixierte Markierung bestehen aus den keramischen Pigmenten und dem anorganischen Bindemittel. Ist die Tinte frei von einem organischen Binder, wird die Markierung beim Fixieren weniger stark beeinflusst, beispielsweise durch ein Zersetzen des organischen Binders und/oder durch ein Ausgasen von Komponenten des eventuell zersetzten organischen Binders, wobei Blasen entstehen können. Außerdem sind Tinten ohne organische Binder kostengünstiger herstellbar.According to at least one embodiment, the ink consists of the solvent, the ceramic pigments and the inorganic binder and the dried ink and the fixed marking consist of the ceramic pigments and the inorganic binder. If the ink is free of an organic binder, the marking is less affected during fixing, for example by decomposition of the organic binder and / or by outgassing of components of the possibly decomposed organic binder, which can result in bubbles. In addition, inks without organic binders can be produced more cost-effectively.

Gemäß zumindest einer Ausführungsform wird eine Form der Markierung bereits im Schritt B) definiert. Das heißt, im Schritt C) erfolgt keine Materialwegnahme aus der bevorzugt getrockneten Tinte oder aus der Markierung, mit welcher ein Informationsgehalt der Markierung verändert wird. Somit ist die Markierung hinsichtlich ihres Informationsgehalts bereits unmittelbar nach dem Schritt B) vollständig.According to at least one embodiment, a shape of the marking is already defined in step B). That is, in step C) there is no removal of material from the preferably dried ink or from the marking, with which an information content of the marking is changed. The information content of the marking is thus already complete immediately after step B).

Gemäß zumindest einer Ausführungsform weist der Bereich mit der Markierung, der im Schritt C) beim Fixieren erhitzt wird, höchstens ein Dreifaches einer Größe der Markierung selbst auf. Das heißt, die Markierung und der erhitzte Bereich sind in etwa gleich groß.According to at least one embodiment, the area with the marking, which is heated in step C) during fixing, has at most three times the size of the marking itself. That is, the marking and the heated area are roughly the same size.

Gemäß zumindest einer Ausführungsform macht der Bereich mit der Markierung höchstens 2 % oder höchstens 10 % des Werkstücks aus. Somit ist die Markierung im Vergleich zum gesamten Werkstück relativ klein.According to at least one embodiment, the area with the marking makes up at most 2% or at most 10% of the Workpiece. The marking is therefore relatively small compared to the entire workpiece.

Gemäß zumindest einer Ausführungsform ist die Markierung mindestens in dem Bereich mit der Markierung über ein Metallblech des Werkstücks erhaben. Das heißt, die Markierung kann ein Relief sein, das sich aus dem Werkstück erhebt.According to at least one embodiment, the marking is raised above a metal sheet of the workpiece at least in the area with the marking. That is, the marking can be a relief that rises from the workpiece.

Gemäß zumindest einer Ausführungsform wird die Markierung in einem Schritt E) nach dem Schritt C), bevorzugt auch nach dem Schritt D), planarisiert. Dieses Planarisieren erfolgt zum Beispiel mittels Lackieren mit einem Lack. Ein solcher Lack kann durchgehend über die Markierung hinweg aufgebracht werden. Der Lack kann für eine zum Auslesen der Markierung verwendete Strahlung durchlässig sein. Alternativ oder zusätzlich ist der Lack zumindest für sichtbares Licht undurchlässig. Ist die Markierung zum Beispiel zum Auslesen im Infraroten Spektralbereich vorgesehen, so kann der Lack im betreffenden Spektralbereich durchlässig sein.According to at least one embodiment, the marking is planarized in a step E) after step C), preferably also after step D). This planarization takes place, for example, by means of painting with a varnish. Such a lacquer can be applied continuously over the marking. The lacquer can be transparent to radiation used to read out the marking. As an alternative or in addition, the lacquer is at least impermeable to visible light. If the marking is intended, for example, for reading in the infrared spectral range, then the lacquer can be permeable in the relevant spectral range.

Gemäß zumindest einer Ausführungsform erfolgt das Fixieren zur Markierung C) mit einem separaten Heizmittel. Das heißt, die Wärmequelle zum Applizieren der erhöhten Temperatur kommt nur zum Fixieren zum Einsatz und nicht auch für andere Prozessschritte bei der Bearbeitung des Werkstücks.According to at least one embodiment, the fixing to the marking C) takes place with a separate heating means. This means that the heat source for applying the increased temperature is only used for fixing and not also for other process steps when machining the workpiece.

Gemäß zumindest einer Ausführungsform umfassen die Tinte und die Markierung mindestens einen Leuchtstoff. Durch den zumindest einen Leuchtstoff kann ein Kontrast zwischen der Markierung und dem Werkstück erhöht werden. Insbesondere bestehen die keramischen Pigmente aus zumindest einem keramischen oder glaskeramischen Leuchtstoff.According to at least one embodiment, the ink and the marking comprise at least one phosphor. A contrast between the marking and the workpiece can be increased by the at least one phosphor. In particular, the ceramic pigments consist of at least one ceramic or glass ceramic phosphor.

Der Leuchtstoff enthält bevorzugt einen oder mehrere der folgenden Stoffe oder besteht hieraus: Eu2+-dotierte Nitride wie (Ca, Sr)AlSiN3:Eu2+, Sr(Ca,Sr)Si2A12N6:Eu2+, (Sr, Ca)AlSiN3*Si2N2O:Eu2+, (Ca, Ba, Sr)2 Si5N8:Eu2+, (Sr,Ca)[LiA13N4]:Eu2+; Granate aus dem allgemeinen System (Gd, Lu, Tb, Y)3 (Al, Ga, D)5(O, X)12:RE mit X = Halogenid, N oder zweiwertiges Element, D = dreiwertiges oder vierwertiges Element und RE = Seltenerdmetalle wie Lu3(Al1-xGax)5O12:Ce3+, Y3(Al1-xGax)5O12:Ce3+; Eu2+-dotierte Sulfide wie (Ca, Sr, Ba) S:Eu2+; Eu2+-dotierte SiONe wie (Ba, Sr, Ca)Si2O2N2:Eu2+; SiAlONe etwa aus dem System LixMyLnzSi12-(m+n)Al(m+n)OnN16-n; beta-SiAlONe aus dem System Si6-xAlzOyN8-y:REz; Nitrido-Orthosilikate wie AE2-x-aRExEuaSiO4-xNx, AE2-x-aRExEuaSi1-yO4-x-2yNx mit RE = Seltenerdmetall und AE = Erdalkalimetall; Orthosilikate wie (Ba, Sr, Ca, Mg)2SiO4:Eu2+; Chlorosilikate wie caaMg(Si04)4C12:Eu2+; Chlorophosphate wie (Sr, Ba, Ca, Mg)10(PO4)6Cl2:Eu2+; BAM-Leuchtstoffe aus dem BaO-MgO-Al2O3-System wie BaMgAl10O17:Eu2+; Halophosphate wie M5 (PO4)3 (Cl, F) : (Eu 2+, Sb3+, Mn2+) ; SCAP-Leuchtstoffe wie (Sr, Ba, Ca)5(PO4)3Cl:Eu2+.The phosphor preferably contains or consists of one or more of the following substances: Eu 2+ -doped nitrides such as (Ca, Sr) AlSiN 3 : Eu 2+ , Sr (Ca, Sr) Si 2 A1 2 N 6 : Eu 2+ , (Sr, Ca) AlSiN 3 * Si 2 N 2 O: Eu 2+ , (Ca, Ba, Sr) 2 Si 5 N 8 : Eu 2+ , (Sr, Ca) [LiAl 3 N 4] : Eu 2+ ; Garnets from the general system (Gd, Lu, Tb, Y) 3 (Al, Ga, D) 5 (O, X) 12 : RE with X = halide, N or divalent element, D = trivalent or tetravalent element and RE = Rare earth metals such as Lu 3 (Al 1-x Ga x ) 5 O 12 : Ce 3+ , Y 3 (Al 1-x Ga x ) 5 O 12 : Ce 3+ ; Eu 2+ -doped sulfides such as (Ca, Sr, Ba) S: Eu 2+ ; Eu 2+ -doped SiONs such as (Ba, Sr, Ca) Si 2 O 2 N 2 : Eu 2+ ; SiAlONe for example from the system Li x M y Ln z Si 12 - (m + n) Al (m + n) O n N 16-n ; beta-SiAlONe from the system Si 6-x Al z O y N 8-y : RE z ; Nitrido-orthosilicates such as AE 2-xa RE x Eu a SiO 4-x N x , AE 2-xa RE x Eu a Si 1- yO 4-x-2y N x with RE = rare earth metal and AE = alkaline earth metal; Orthosilicates such as (Ba, Sr, Ca, Mg) 2 SiO 4 : Eu 2+ ; Chlorosilicates such as a Mg (Si0 4 ) 4 C1 2 : Eu 2+ ; Chlorophosphates such as (Sr, Ba, Ca, Mg) 10 (PO 4 ) 6 Cl 2 : Eu 2+ ; BAM phosphors from the BaO-MgO-Al 2 O 3 system such as BaMgAl 10 O 17 : Eu 2+ ; Halophosphates such as M 5 (PO 4 ) 3 (Cl, F): ( Eu 2+ , Sb 3+ , Mn 2+ ); SCAP phosphors such as (Sr, Ba, Ca) 5 (PO 4 ) 3 Cl: Eu 2+ .

Der Leuchtstoff kann zu einer Verkürzung der Wellenlänge einer Anregungsstrahlung, auch als Upconversion bezeichnet, eingerichtet sein und beispielsweise infrarotes Licht in sichtbares Licht umwandeln. Alternativ kann der Leuchtstoff kurzwelliges Licht in langwelliges Licht umwandeln. Es ist möglich, dass der Leuchtstoff insbesondere durch die Temperaturen während der Warmumformung in seinen Lumineszenzeigenschaften verändert wird. Hierdurch ist auch eine Qualitätskontrolle erzielbar, ob die Warmumformung bei korrekten Prozessparametern erfolgt ist.The luminescent material can be set up to shorten the wavelength of an excitation radiation, also referred to as upconversion, and, for example, convert infrared light into visible light. Alternatively, the phosphor can convert short-wave light into long-wave light. It is possible that the phosphor is in its Luminescence properties is changed. In this way, a quality control can also be achieved as to whether the hot forming has taken place with the correct process parameters.

Gemäß zumindest einer Ausführungsform handelt es sich bei dem Leuchtstoff um ein thermolumineszierendes Material, das heißt um ein bei Erreichen einer Schwellentemperatur lumineszierendes Material. Bevorzugt liegt die Schwellentemperatur bei mindestens 125 °C oder 175 °C. Der Leuchtstoff umfasst dann als Dotierung und/oder als Bestandteil eines Kristallgitters oder eines Wirtsgitters bevorzugt eines oder mehrere der folgenden Elemente: Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb. Besonders bevorzugt handelt es sich bei dem thermolumineszierenden Leuchtstoff um NaYF4:Er, Yb. Die Verwendung solcher Leuchtstoffe ist zum Beispiel in der Druckschrift DE 10 2017 125 006 A1 beschrieben.According to at least one embodiment, the luminescent material is a thermoluminescent material, that is to say a material that luminesces when a threshold temperature is reached. The threshold temperature is preferably at least 125 ° C or 175 ° C. The phosphor then preferably comprises one or more of the following elements as doping and / or as a component of a crystal lattice or a host lattice: Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb. The thermoluminescent phosphor is particularly preferably NaYF 4 : Er, Yb. The use of such phosphors is for example in the document DE 10 2017 125 006 A1 described.

Darüber hinaus wird ein Werkstück angegeben. Das Werkstück ist mit einem Verfahren markiert, wie in Verbindung mit einer oder mehrerer der oben genannten Ausführungsformen angegeben.A workpiece is also specified. The workpiece is marked with a method as specified in connection with one or more of the above-mentioned embodiments.

Das erfindungsgemäß hergestellte Werkstück weist die Markierung auf, wobei das Werkstück nur im Bereich der Markierung eine Verfärbung und/oder eine veränderte Materialstruktur aufweist, die durch ein Erhitzen auf eine Temperatur von mindestens 400 °C im Schritt C) verursacht ist. Das Werkstück ist bevorzugt ein warmumgeformtes Metallteil oder ein Metallrohling, der für eine Warmumformung vorgesehen ist.The workpiece produced according to the invention has the marking, the workpiece having a discoloration and / or a changed material structure only in the area of the marking, which is caused by heating to a temperature of at least 400 ° C. in step C). The workpiece is preferably a hot-formed metal part or a metal blank which is provided for hot forming.

Über die Materialien, aus denen die Markierung zusammengesetzt ist, lässt sich die minimale Temperatur zum Fixieren der Markierung bestimmen. Über die lokale Verfärbung und/oder veränderte Materialstruktur des Werkstücks an der Markierung lässt sich bestimmen, in welchem räumlichen Bereich die Temperatur zum Fixieren am Werkstück appliziert wurde, ob also nur ein lokales Erhitzen erfolgte. Beispielsweise äußerst sich das lokale Erhitzen beim Fixieren der Markierung in einer Anlauffarbe um die Markierung herum.The minimum temperature for the Determine the fixation of the marking. The local discoloration and / or changed material structure of the workpiece on the marking can be used to determine in which spatial area the temperature was applied to the workpiece for fixing, i.e. whether only local heating took place. For example, the local heating is extreme when the marking is fixed in a tarnishing color around the marking.

Nachfolgend wird ein hier beschriebenes Verfahren unter Bezugnahme auf die Zeichnung näher erläutert. Gleiche Bezugszeichen geben dabei gleiche Elemente in den einzelnen Figuren an. Es sind jedoch keine maßstäblichen Bezüge dargestellt, vielmehr können einzelne Elemente zum besseren Verständnis übertrieben groß dargestellt sein.A method described here is explained in more detail below with reference to the drawing. The same reference symbols indicate the same elements in the individual figures. However, no references to scale are shown; rather, individual elements can be shown exaggeratedly large for better understanding.

Es zeigen:

Figuren 1
bis 6 schematische perspektivische Darstellungen von Schritten eines hier beschriebenen Verfahrens zur Markierung von Werkstücken,
Figuren 7
bis 9 schematische Schnittdarstellungen von Schritten eines hier beschriebenen Verfahrens zur Markierung von Werkstücken,
Figur 10
eine schematische perspektivische Darstellung eines Fixierschritts eines hier beschriebenen Verfahrens,
Figur 11
eine schematische perspektivische Darstellung eines Fixierschritts eines nicht erfindungsgemäßen Verfahrens, und
Figuren 12 bis 14
schematische perspektivische Darstellungen von Schritten von nicht erfindungsgemäßen Verfahren.
Show it:
Figures 1
through 6 are schematic perspective representations of steps in a method described here for marking workpieces,
Figures 7
through 9 are schematic sectional representations of steps in a method described here for marking workpieces,
Figure 10
a schematic perspective illustration of a fixing step of a method described here,
Figure 11
a schematic perspective illustration of a fixing step of a method not according to the invention, and
Figures 12 to 14
schematic perspective representations of steps of methods not according to the invention.

In den Figuren 1 bis 6 ist ein Ausführungsbeispiel eines Verfahrens zur Markierung von Werkstücken 1 illustriert. Gemäß Figur 1 wird ein Metallblech 11 mit einer Werkstückoberfläche 10 bereitgestellt. Bei dem Metallblech 11 handelt es sich bevorzugt um ein Stahlblech, zum Beispiel um ein gestanztes, aber noch ebenes Blech.In the Figures 1 to 6 an embodiment of a method for marking workpieces 1 is illustrated. According to Figure 1 a metal sheet 11 with a workpiece surface 10 is provided. The metal sheet 11 is preferably a steel sheet, for example a stamped but still flat sheet.

In Figur 2 ist gezeigt, dass auf die Werkstückoberfläche 10 eine Tinte 20 für eine Markierung 2 aufgedruckt wird. Das Drucken erfolgt mit einer Druckdüse 5. Somit kann die Markierung 2 strukturiert mittels Tintenstrahldrucken erzeugt werden. Die Markierung 2 wird hierbei bereits im Wesentlichen mit ihrer endgültigen Gestalt erzeugt. Die Markierung 2 ist beispielsweise ein Schriftzug.In Figure 2 it is shown that an ink 20 for a marking 2 is printed on the workpiece surface 10. The printing takes place with a printing nozzle 5. The marking 2 can thus be produced in a structured manner by means of inkjet printing. The marking 2 is in this case already produced essentially with its final shape. The marking 2 is, for example, a lettering.

Nach dem Aufdrucken kann die noch feuchte Tinte 20 bevorzugt bei Raumtemperatur zu einer getrockneten Tinte 20' trocknen. Die getrocknete Tinte 20' haftet bevorzugt wischfest auf der Werkstückoberfläche 10, würde jedoch bei stärkerer Reibung oder bei Einfluss von Lösungsmitteln wieder verschwinden.After printing, the still moist ink 20 can preferably dry at room temperature to give a dried ink 20 '. The dried ink 20 'preferably adheres to the workpiece surface 10 in a smudge-proof manner, but would disappear again in the event of greater friction or the influence of solvents.

Gemäß Figur 3 wird die getrocknete Tine 20' mit Hilfe eines Bestrahlungskopfs 31 mit ultravioletter Strahlung bestrahlt. Die Bestrahlung konzentriert sich auf einen kleinen Bereich 3 um die spätere, fertige Markierung 2. Aufgrund der Bestrahlung wird die getrocknete Tine 20' stark erhitzt, zum Beispiel auf ungefähr 600 °C. Dadurch wird die Tinte 20' zur Markierung 2 fixiert. Die Bestrahlung kann unstrukturiert und zusammenhängend über die ganze Markierung 2 hinweg erfolgen.According to Figure 3 the dried ink 20 'is irradiated with ultraviolet radiation with the aid of an irradiation head 31. The irradiation is concentrated on a small area 3 around the later, finished marking 2. As a result of the irradiation, the dried ink 20 'is strongly heated, for example to approximately 600.degree. The ink 20 ′ is thereby fixed to the marking 2. The irradiation can take place in an unstructured and contiguous manner over the entire marking 2.

Das heißt, die Markierung 2 wird dann nicht etwa mit einem Laserstrahl abgerastert.This means that the marking 2 is then not scanned with a laser beam, for example.

Die Bestrahlung erfolgt zum Beispiel mit UV-Strahlung um 360 nm mit einer Energiedichte von ungefähr 8 J/cm2. Die Bestrahlung dauert zum Beispiel lediglich rund 100 µs an. Damit lassen sich thermische Belastungen des Metallblechs 11 außerhalb des Bereichs 3 mit der Markierung 2 stark reduzieren. Bei der verwendeten Strahlung handelt es sich insbesondere um inkohärente Strahlung, zum Beispiel aus einer Blitzlampe.The irradiation takes place, for example, with UV radiation around 360 nm with an energy density of approximately 8 J / cm 2 . The irradiation lasts, for example, only around 100 µs. In this way, thermal loads on the metal sheet 11 outside the area 3 with the marking 2 can be greatly reduced. The radiation used is in particular incoherent radiation, for example from a flash lamp.

In Figur 4 ist die fertige, fixierte Markierung 2 gezeigt. Aufgrund der Bestrahlung und der damit verbundenen Temperaturerhöhung in dem Bereich 3 ist es möglich, dass um die eigentliche Markierung 2 herum eine Farbveränderung 6 auftritt. Die Farbveränderung 6 ist jedoch auf ein kleines Gebiet um die Markierung 2 herum begrenzt.In Figure 4 the finished, fixed marker 2 is shown. Due to the irradiation and the associated increase in temperature in the area 3, it is possible that a color change 6 occurs around the actual marking 2. The color change 6, however, is limited to a small area around the marking 2.

Im optionalen Schritt der Figur 5 erfolgt eine Warmumformung des Werkstücks 1. Die fixierte Markierung 2 kann in Gebieten des Werkstücks 1 angebracht sein, die von der Warmumformung betroffen sind. Alternativ befindet sich die Markierung 2 außerhalb von Gebieten, in denen eine Warmumformung erfolgt. Durch die Warmumformung wird die Markierung 2 in ihrer Lesbarkeit nicht oder nur gering beeinträchtigt.In the optional step of the Figure 5 a hot forming of the workpiece 1 takes place. The fixed marking 2 can be applied in areas of the workpiece 1 that are affected by the hot forming. Alternatively, the marking 2 is located outside of areas in which hot forming takes place. The legibility of the marking 2 is not impaired or only slightly impaired by the hot forming.

Mit dem hier beschriebenen Verfahren ist die Markierung 2 also bereits in einem frühen Fertigungsstadium des Werkstücks 1 und unabhängig von anderen Prozessschritten anbringbar und unverlierbar mit dem Bauteil verbunden. Damit ist eine effiziente und zuverlässige Nachverfolgung des Werkstücks auch über lange Prozessketten hinweg möglich.With the method described here, the marking 2 can therefore already be attached and cannot be lost with the component in an early manufacturing stage of the workpiece 1 and independently of other process steps. This enables efficient and reliable tracking of the workpiece, even across long process chains.

Gemäß dem optionalen Schritt der Figur 6 wird auf die Werkstückoberfläche 10 bereichsweise oder ganzflächig eine Beschichtung 4 aufgebracht. Bei der Beschichtung 4 handelt es sich zum Beispiel um einen Lack. Es ist möglich, dass für das menschliche Auge die Markierung 2 durch die Beschichtung 4 verborgen wird, jedoch kann die Beschichtung optional noch maschinenlesbar sein.According to the optional step of the Figure 6 a coating 4 is applied to the workpiece surface 10 in areas or over the whole area. The coating 4 is, for example, a lacquer. It is possible for the marking 2 to be hidden from the human eye by the coating 4, but the coating can optionally still be machine-readable.

In den Figuren 7 bis 9 ist die Bildung der Markierung 2 aus der Tinte 20 näher erläutert. Gemäß Figur 7 wird die Tinte 20 auf das Werkstück 1 aufgebracht. Die Tinte 20 ist dabei aus keramischen Pigmenten 21, Partikeln eines anorganischen Bindemittels 22, einem organischen Binder 23, einem Lösungsmittel 24 und einem Dispergierhilfsmittel 25 zusammengesetzt.In the Figures 7 to 9 the formation of the marking 2 from the ink 20 is explained in more detail. According to Figure 7 the ink 20 is applied to the workpiece 1. The ink 20 is composed of ceramic pigments 21, particles of an inorganic binder 22, an organic binder 23, a solvent 24 and a dispersing aid 25.

In Figur 8 ist die getrocknete Tinte 20' illustriert, die kein Lösungsmittel 24 mehr aufweist. Die Pigmente 21 und das Bindemittel 22 sowie das optional vorhandene Dispergierhilfsmittel 25 werden über den organischen Binder 23 zusammengehalten, sodass die getrocknete Tinte 20' wischfest an dem Werkstück 1 angebracht ist.In Figure 8 the dried ink 20 ′ is illustrated, which no longer contains any solvent 24. The pigments 21 and the binder 22 as well as the optionally present dispersing aid 25 are held together by the organic binder 23 so that the dried ink 20 ′ is attached to the workpiece 1 in a smudge-proof manner.

Gemäß Figur 9 ist das Sintern und Fixieren zu der Markierung 2 erfolgt. Der organische Binder 23 und das Dispergierhilfsmittel sind nicht mehr vorhanden oder nur noch in Spuren vorhanden, die keine dezidierte Funktion mehr erfüllen. Durch das Sintern und/oder Fixieren werden bevorzugt zusammenhängende Gebiete der Markierung 2 für einzelne Zeichen gebildet. Innerhalb eines zusammenhängenden Gebiets zeigt die Markierung 2 für einen Betrachter und/oder für eine Kamera bevorzugt einen homogenen Farbeindruck auf.According to Figure 9 the sintering and fixing to mark 2 has taken place. The organic binder 23 and the dispersing aid are no longer present or only present in traces which no longer fulfill a specific function. By sintering and / or fixing, contiguous areas of the marking 2 are preferably formed for individual characters. Within a contiguous area, the marking 2 preferably shows a homogeneous color impression for an observer and / or for a camera.

Die zusammenhängenden Gebiete können als glatte Erhebungen über das Werkstück gebildet sein. Bevorzugt sind die zusammenhängenden Gebiete durch eine Glaskeramik gebildet, die aus den Pigmenten 21 und dem Bindemittel 22 erzeugt ist.The contiguous areas can be formed as smooth elevations over the workpiece. The contiguous areas are preferably formed by a glass ceramic which is produced from the pigments 21 and the binder 22.

Die Tinte 20, wie in den Figuren 7 bis 9 beschrieben, kann auch in allen anderen Ausführungsbeispielen verwendet werden.The ink 20, as in Figs Figures 7 to 9 can also be used in all other exemplary embodiments.

In den Figuren 10 und 11 sind Alternativen zum Schritt des Erhitzens der Figur 2 gezeigt. Gemäß Figur 10 werden Kontaktnadeln 32 auf das elektrisch leitfähige Werkstück 1 aufgesetzt, wobei mehr als zwei Kontaktnadeln 32 verwendet werden können. Über die Kontaktnadeln 32 werden im Werkstück 1 elektrische Ströme in dem Gebiet 3 erzeugt, die zu einer lokalen starken Erhitzung des Werkstücks 1 und damit der getrockneten Tine 20' führen. Hierdurch kann das Fixieren zur Markierung 2 durchgeführt werden. Alternativ können kontaktlos über Magnetfelder insbesondere Wirbelströme in dem Werkstück zum Fixieren verwendet werden.In the Figures 10 and 11 are alternatives to the step of heating the Figure 2 shown. According to Figure 10 contact needles 32 are placed on the electrically conductive workpiece 1, with more than two contact needles 32 being able to be used. Via the contact needles 32, electrical currents are generated in the workpiece 1 in the area 3, which lead to a strong local heating of the workpiece 1 and thus the dried ink 20 '. This enables the fixing to the marking 2 to be carried out. Alternatively, eddy currents in particular can be used in the workpiece for fixing in a contactless manner via magnetic fields.

Demgegenüber wird gemäß dem nicht erfindungsgemäßen Verfahren der Figur 11 eine Heizspitze 33 nahe an die Tinte 20 oder an die optional getrocknete Tinte 20' herangeführt. Die Heizspitze 33 wird erhitzt, wodurch die Tinte 20 getrocknet und erhitzt wird oder die bereits getrocknete Tinte 20' erhitzt wird und zur Markierung 2 fixiert wird. Die Heizspitze 33 wird bevorzugt nur über der getrockneten Tinte 20' betrieben. Bevorzugt wird die gesamte Markierung 2 in einem einzigen Heizschritt mit der Heizspitze 33 fertiggestellt.In contrast, according to the method not according to the invention Figure 11 a heating tip 33 is brought close to the ink 20 or to the optionally dried ink 20 '. The heating tip 33 is heated, whereby the ink 20 is dried and heated or the already dried ink 20 ′ is heated and fixed to the marking 2. The heating tip 33 is preferably operated only over the dried ink 20 '. The entire marking 2 is preferably completed in a single heating step with the heating tip 33.

Zudem ist in Figur 10 veranschaulicht, dass die Markierung 2 durch einen Strichcode gebildet ist. In Figur 11 ist die Markierung 2 ein Matrix-Code. Solche Arten von Markierungen 2 können entsprechend auch in allen anderen Ausführungsbeispielen verwendet werden.In addition, in Figure 10 illustrates that the marking 2 is formed by a bar code. In Figure 11 mark 2 is a matrix code. Such types of markings 2 can correspondingly also be used in all other exemplary embodiments.

Gemäß den Figuren 2, 10 und 11 wird jeweils ein separates Heizmittel 31, 32, 33 verwendet, das dezidiert nur zum Fixieren der getrockneten Tinte 20' oder zum Trocknen und Fixieren der Tinte 20 dient. Demgegenüber wird die Fixierung zur Markierung 2 gemäß der nicht erfindungsgemäßen Verfahren der Figuren 12 bis 14 mit einem weiteren Prozessschritt kombiniert.According to the Figures 2 , 10 and 11 a separate heating means 31, 32, 33 is used in each case, which is used specifically only for fixing the dried ink 20 ′ or for drying and fixing the ink 20. In contrast, the fixation for the marking 2 according to the method not according to the invention of FIG Figures 12 to 14 combined with a further process step.

So wird gemäß Figur 12 das Werkstück 1 mit der nur schematisch angedeuteten getrockneten Tinte 20' bereitgestellt. Im Schritt der Figur 13 wird das Werkstück 1 mit einem Verformwerkzeug 34a, 34b verformt. Dabei wird zumindest das Verformwerkzeug 34b, das die getrocknete Tinte 20' abdeckt, geheizt. Das resultierende, warmumgeformte Werkstück 1 mit der fertigen Markierung 2 ist in Figur 14 dargestellt.So is according to Figure 12 the workpiece 1 is provided with the dried ink 20 ', which is only indicated schematically. In the step of the Figure 13 the workpiece 1 is deformed with a deforming tool 34a, 34b. In this case, at least the deforming tool 34b, which covers the dried ink 20 ', is heated. The resulting, hot-formed workpiece 1 with the finished marking 2 is shown in FIG Figure 14 shown.

Die in den Figuren gezeigten Komponenten folgen, sofern nicht anders kenntlich gemacht, bevorzugt in der angegebenen Reihenfolge jeweils unmittelbar aufeinander. Sich in den Figuren nicht berührende Schichten sind bevorzugt voneinander beabstandet. Soweit Linien parallel zueinander gezeichnet sind, sind die entsprechenden Flächen bevorzugt ebenso parallel zueinander ausgerichtet. Ebenfalls, soweit nicht anders kenntlich gemacht, sind die relativen Positionen der gezeichneten Komponenten zueinander in den Figuren korrekt wiedergegeben.Unless otherwise indicated, the components shown in the figures preferably follow one another in the specified order. Layers that do not touch one another in the figures are preferably spaced apart from one another. As far as lines are drawn parallel to one another, the corresponding surfaces are preferably also aligned parallel to one another. Likewise, unless otherwise indicated, the relative positions of the components drawn are shown correctly in the figures.

BezugszeichenlisteList of reference symbols

11
Werkstückworkpiece
1010
WerkstückoberflächeWorkpiece surface
1111th
Metallblech (Stahlblech)Sheet metal
22
Markierungmark
2020th
Tinteink
20'20 '
getrocknete Tintedried ink
2121
keramische Pigmenteceramic pigments
2222nd
anorganisches Bindemittelinorganic binder
2323
organischer Binderorganic binder
2424
Lösungsmittelsolvent
2525th
DispergierhilfsmittelDispersing aid
33
Bereich mit der Markierung, der erhitzt wirdArea with the mark that is being heated
3131
BestrahlungskopfIrradiation head
3232
KontaktnadelContact needle
3333
HeizspitzeHeating tip
3434
VerformwerkzeugDeform tool
44th
Beschichtung (Lack)Coating
55
DruckdüsePressure nozzle
66th
VerfärbungDiscoloration

Claims (14)

  1. A method for marking workpieces (1) comprising the steps of:
    A) providing the at least one workpiece (1),
    B) locally applying an ink (20) for a marking (2) to the workpiece (1),
    C) fixing the ink (20) to produce the marking (2),
    characterized in that
    the workpiece (1) is heated locally in a region (3) with the marking (2) during fixing and a temperature of at least 400 °C is applied to the ink (20) when fixing occurs, and fixing is done in step C)
    - by means of a radiation flash and radiation of the radiation flash is incoherent and is absorbed in the ink (20) and/or on a workpiece surface (10) and as a result the temperature is applied for fixing, or
    - contact-free and by means of induction, or
    - by means of an electrical resistance, wherein electrodes are attached to the workpiece (1).
  2. The method according to the preceding claim,
    wherein the ink (20) contains ceramic pigments (21) which bring about a coloring and/or a contrast of the marking (2) with respect to the workpiece (1),
    wherein the ink (20) additionally contains an inorganic binder (22) which is also contained in the finished marking (2), and
    wherein the ink (20) is applied by means of a printing process.
  3. The method according to claim 2,
    wherein in step B) the ink (20) consists of a solvent (24), the ceramic pigments (21) and the inorganic binder (22) and optionally of a dispersing aid (25), and after step C) the marking (2) consists of the ceramic pigments (21) and the inorganic binder (22).
  4. The method according to claim 1 or 2,
    wherein in step B) the ink (20) comprises an organic binder (23), such that the dried ink (20') is wiping-proof already before step C) on account of the organic binder (23).
  5. The method according to one of the preceding claims,
    wherein in step C) the temperature of at least 400 °C is applied for at most 1 min.
  6. The method according to one of the preceding claims,
    wherein the workpiece (1) is an iron sheet or a steel sheet (11),
    wherein the temperature during fixing in step C) is between 500 °C and 1200 °C inclusive,
    wherein, after step C), the workpiece (1) undergoes hot forming in a step D), and
    wherein the marking (2) is still readable after step D).
  7. The method according to one of the preceding claims,
    wherein the fixing in step C) takes place by the radiation flash,
    wherein the radiation of the radiation flash is predominantly ultraviolet radiation.
  8. The method according to any one of claims 1 to 6,
    wherein the fixing in step C) takes place in a contactless manner by means of the induction.
  9. The method according to one of the preceding claims,
    wherein a shape of the marking (2) is already defined in step B), so that in step C) no material removal from the ink (20) or from the marking (2), which changes an information content of the marking (2), takes place.
  10. The method according to one of the preceding claims,
    wherein the region (3) with the marking (2), which is heated in step C) during fixing, has at most a triple of a size of the marking (2) itself,
    wherein the region (3) with the marking (2) makes up at most 10% of the workpiece (1).
  11. The method according to one of the preceding claims,
    wherein the marking (2) is raised above a metal sheet (11) of the workpiece (1) at least in the region (3) with the marking (2) .
  12. The method according to one of the preceding claims,
    wherein the marking (2) is planarized in a step E) after step C),
    wherein in step E) a lacquer (4) is applied continuously across the marking (2).
  13. The method according to one of the preceding claims,
    wherein in step C) a heating means (31, 32, 33) is used, which is used for no further process steps for machining the workpiece (1).
  14. The method according to one of the preceding claims,
    wherein the ink (20) and the marking (2) comprise at least one phosphor.
EP18205412.2A 2018-11-09 2018-11-09 Method for marking workpieces Active EP3650238B1 (en)

Priority Applications (2)

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ES18205412T ES2904878T3 (en) 2018-11-09 2018-11-09 Workpiece Marking Procedure
EP18205412.2A EP3650238B1 (en) 2018-11-09 2018-11-09 Method for marking workpieces

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Application Number Priority Date Filing Date Title
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DE102021121983A1 (en) 2021-08-25 2023-03-02 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Ceramic component and manufacturing method therefor
DE102022207444A1 (en) 2022-07-21 2024-02-01 Volkswagen Aktiengesellschaft Process for producing components from a powdery material
DE102023116057B3 (en) 2023-06-20 2024-09-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Method for reading a marking

Citations (1)

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DE2617671B2 (en) * 1975-04-25 1978-06-08 Hoogovens Ijmuiden B.V., Ijmuiden (Niederlande) Marking compound for hot metal objects

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US6660184B2 (en) 2001-12-13 2003-12-09 Osram Sylvania Inc. Phosphor paste compositions
DE102015107744B3 (en) 2015-05-18 2016-07-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for marking workpieces and a workpiece produced in this way
EP3109058A3 (en) 2015-06-26 2017-01-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for marking workpieces and marked workpiece
DE102015119618B3 (en) * 2015-11-13 2017-03-02 Hochschule Offenburg Digital printing process for ceramic paints
DE102016015772A1 (en) * 2016-10-05 2018-04-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Workpiece and method for marking workpieces
DE102016118842B3 (en) * 2016-10-05 2017-12-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Method for marking workpieces and workpiece

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2617671B2 (en) * 1975-04-25 1978-06-08 Hoogovens Ijmuiden B.V., Ijmuiden (Niederlande) Marking compound for hot metal objects

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