Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/20—Direct sintering or melting
  • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/30—Process control
  • B22F10/36—Process control of energy beam parameters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
  • B22F10/30—Process control
  • B22F10/36—Process control of energy beam parameters
  • B22F10/368—Temperature or temperature gradient, e.g. temperature of the melt pool
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
  • B22F12/10—Auxiliary heating means
  • B22F12/13—Auxiliary heating means to preheat the material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
  • B22F12/10—Auxiliary heating means
  • B22F12/17—Auxiliary heating means to heat the build chamber or platform
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
  • B22F12/90—Means for process control, e.g. cameras or sensors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y50/00—Data acquisition or data processing for additive manufacturing
  • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/25—Process efficiency

Definitions

• the invention relates to a method for additive production of a component, in particular for a turbomachine, in which successively provided a plurality of layers of a particular powdery material and each materi allage with at least one energy beam, in particular at least one laser beam according to a predetermined component geometry scanned is, with an additional heating ei nes already manufactured component section and / or the ever-provided material layer and / or a working platform on which the component is constructed takes place.
• the invention relates to a device for ad ditive production of a component, in particular for a turbomachine, comprising
• Means for providing superimposed, preferably powdered material layers in the working area are provided.
• tion which is designed and set up to emit at least one energy, in particular laser beam and materials provided in the work area with the at least one energy, in particular laser, beam according to a predetermined component geometry
• the invention relates to a component, in particular for a turbomachine.
• a plurality of particular powdery layers of material are successively provided one above the other and each layer is scanned by one or more energy beams, in particular laser or electron beams according to a predetermined component geometry and thereby locally melted or sintered.
• energy beams in particular laser or electron beams according to a predetermined component geometry and thereby locally melted or sintered.
• additive manufacturing processes include selective laser melting (SLM) or selective electron beam melting (SEBM) and selective laser or electron beam sintering (English: Selective Laser Singing).
• SLS or Selective Electron Beam Sintering - SEBS) from the powder bed is called laser powder overlay welding (LPA).
• the layer-wise construction of a component takes place on a height-adjustable work platform which forms the bottom of a production cylinder and means are provided for providing powder.
• V erlagen the one next to the work platform to parent storage cylinder with a liftable floor and egg ne trained as a squeegee distribution device, by means of which powder can be conveyed from the stock in the production cylinder and smoothed, include.
• the powder provided is pressed from this gradually by lifting the bottom up and with the Ra angle in layers on the adjacent building platform trans feriert and distributed there.
• resistive heating inductive heating
• IR heating inductive heating
• electron beam heating electron beam heating
• the latter type of heating is seen for example in accordance with DE 10 2015 201 637 Al in the context of SLM from the powder bed before.
• means for additional heating are IN ANY, the nenstrahletti arranged above the powder bed electric, by means of which an electron beam can be directed from above perpendicular to the powder bed include.
• the electron beam is directed to the material layer before, during and / or after the laser melting.
• the laser source is located on the side of the powder bed and the scan beam is directed diagonally from the side towards the powder bed, so that the electron beam is not blocked.
• DE 10 212 206 122 Al shows, in the context of egg nes additive manufacturing process, such as the Laserpulverauf contract welding or selective irradiation of a powder bed to perform an additional, specifically inductive heating of herzustel sirloin component.
• the means for additional inductive heating also comprise at least one coil
• the DE 10 212 206 122 Al provides that the at least one coil is movable and their position is changed during the additive production.
• the additional heating makes it possible to obtain better results, in particular the preservation of components with improved properties, since the formation of cracks is avoided or at least reduced - even when using materials which are difficult to weld.
• This object is achieved in a method of the type mentioned fact that for at least one, in particular for each material layer, the temperature distribution on the surface on which the material layer is provided, in particular before provision of the position metrologically it is summarized, and / or the temperature distribution is detected on the Oberflä surface of the layer provided by measurement, and that in the context of scanning the material layer, the amount of energy introduced with the at least one energy beam depending on the detected temperature distribution on the upper surface on which the situation is provided, and / or in dependence the detected temperature distribution on the Oberflä surface of the layer is varied, in particular such that an inhomogeneity of the temperature distribution is reduced or compensated.
• the present invention is based on the finding that in the context of additional heating or heating in Additi ven production process, which in particular allows processing even of difficult-to-weld materials, usually no homogeneous temperature distribution is obtained.
• an at least to some extent inhomogeneous temperature profile results in the respectively provided material. allage, or an underlying hergestell th component section with which various disadvantages are connected.
• Significant disadvantages of an inhomogeneous temperature distribution are, for example, an uneven temperature expansion in the material and associated inaccuracies in the application of material, uncontrollable lateral heat flow in the resulting component and risk of cracking due to stresses in remote component regions.
• the component quality can be adversely affected, process-related defects can not be reliably avoided, a slowing down of the construction process may become necessary and it may result in limiting conditions with regard to design freedom.
• the additional heating and scanning, in particular on melting or sintering process with the at least one energy beam are optimally matched to each other, specifically the we least one energy beam is selectively controlled to Inho mogenticianen that themselves due to the additional, as inductive heating adjust adjust.
• the flexibility of the at least one energy beam is used according to the invention to absorb an uneven temperature distribution.
• the at least one energy beam, scanned with the material layer is controlled compensating depending on the measurement.
• the introduced via the at least one energy, in particular laser energy input during the scanning process by varying suitable parameters is adjusted. In particular, the amount of energy introduced per volume and / or time unit is varied.
• the procedure according to the invention results in a particularly homogeneous introduction of energy and thus a clear quality. improved.
• the process stability is increased and the requirements for the concept for the additional heating can be reduced. If, for example, an existing heating concept delivers only a comparatively inhomogeneous temperature distribution, this can be tolerated and compensated for in a comparatively simple manner by an adapted energy beam control alone.
• Another great advantage of the procedure according to the invention is that fast heating times and thus a reduction of the construction time and costs can be achieved.
• the materials from which components can be manufactured additive by carrying out the inventions to the invention process may in particular be all inductively heatable metals, preferably nickel-based, iron-based or Cobaltbasiswerkstof fe.
• the metrological detection of the temperature distribution on the surface of a material layer or on the surface on which it is provided, for example, can take place at predetermined, suitable times, for example before or after the provision of a layer. Particularly preferably it follows the metrological detection and / or the evaluation of the detected temperature distribution, such as a detected Tem perature image in temporal proximity to the subsequent Scanvor gang with at least one energy beam.
• the temperature distribution in the manner of a conven- tional video continuously or quasi-continuously recorded and then in particular single images boastge be resorted.
• a plurality of successive recordings but with a high temporal resolution is to understand, for example, several o or several ten frames per second.
• a block-by-block approach in which a temperature distribution is detected per section or a completely continuous recording, in which an adjustment is made to control the energy input, eg the power with each recorded temperature image of the camera.
• the detection of the temperature distribution takes place according to a further embodiment at least over that area of the surface over which the area of the respective material layer to be scanned extends. It can also be provided that the measured area "mitwandert", as the tempera ture established always over a range of predetermined extent occurs, which always includes the current impact point at least ei Nes energy beam and / or that area, the additional Lich in particular inductively heated or re is defined to this.
• the additional Lich in particular inductively heated or re is defined to this.
• the temperature distribution on the surface of a work platform on which the first layer is provided is present for the first and lowest materials Provision of the first layer is detected by measurement, and within the scope of the scanning of the first layer, the amount of energy introduced with the at least one energy beam is varied depending on the detected temperature distribution on the surface of the working platform.
• a further embodiment of the method according to the invention is characterized in that the amount of energy introduced with the at least one energy beam during the scanning process Ganges is varied by the intensity and / or the power and / or the pulse duration and / or the beam or focus diameter and / or the traversing speed of the least one energy beam, and / or the density of Scanvekto ren, in particular scan lines , along which the at least one energy beam is moved over the material layer, is varied during the scanning process.
• These parameters have proven to be particularly suitable for the energy yield during the scanning process as a function of a detected temperature distribution to compensate for inhomogeneities of this Anlagenpas sen. If, for example, the energy beam, in particular laser line, is increased while the energy beam is moved along a scan line over a provided material layer, a temperature gradient resulting in the direction of this scan line can be compensated for and swept around.
• the temperature distribution at the surface on which the material layer is provided is detected by measurement, by means of egg ner thermal camera, a temperature image of this surface is taken up.
• the temperature distribution on the surface of the material layer can be detected metrologically by using a Ther mogro a temperature image of the surface of the material layer is recorded.
• a thermal camera is to be understood in particular as any type of camera which makes it possible to determine the temperatures of object surfaces in a contactless and flat manner, such as thermal imaging cameras.
• a thermal camera works in particular analogous to a camera in the visual wavelength range, but as a rule recordings are made in the infrared wavelength range. Accordingly, a thermal camera usually has a particularly in inf raroten wavelength range sensitive detector. The wavelength of a camera used, in particular the detector of such, expediently corresponds insofar as the target temperature of the heating, that a heat radiation sufficient in the wavelength range of the camera is removed. will be in order to be detected by the camera.
• the intensity of the emitted radiation correlates with the temperature, so that can be converted by a calibration of the received radiation intensity on the temperature umgerech net.
• a temperature image is taken, this can be evaluated, in which case preferably the energy introduced with the at least one energy beam is varied as a function of the result of the evaluation.
• Temperature images obtained are in particular in the form of temperature values for each camera pixel and can be used for further processing.
• the temperatures can be displayed, for example, in the form of false color or grayscale images.
• An associated scale can then assign gray or color values to temperatures.
• At least one temperature gradient is determined or calculated on the basis of a temperature image.
• the energy introduced with the at least one energy beam can then be varied during the scanning process as a function of the calculated temperature gradient.
• the energy beam, in particular laser, line along a scan vector, in particular along a scan line to be modulated such that an inhomogeneity of a detected temperature distribution is counteracted.
• the variation during a scanning process may in particular be such that where, according to the detected temperature distribution, there is a comparatively lower temperature, the amount of energy introduced by the at least one energy beam is increased, and / or where, according to the detected temperature distribution, an im Comparison higher temperature is present, which is reduced by the at least one energy beam introduced amount of energy.
• comparison means then in particular compared to another location of a material layer which has already been scanned with the at least one energy beam.
• An increase in the amount of energy introduced can be achieved, for example, by increasing the intensity and / or the power of at least one energy beam and / or increasing the density of scan vectors, in particular scan lines, along which at least one energy beam is moved over the material position, and / or a reduction in the Verfahrge speed at least one energy beam can be achieved.
• a reduction in the amount of energy introduced can be achieved by reducing the intensity and / or the power of at least one energy beam and / or reducing the density of scan vectors, in particular scan lines, along which at least one energy beam is moved over the material layer, and / or an increase in the travel speed at least one energy beam can be achieved.
• the power of the at least one energy beam can be modulated, for example, along a scan vector and / or from scan vector to scan vector as a function of a detected temperature distribution.
• the additional heating of the respectively provided material layer and / or of an already produced component section and / or a working platform on which the component is constructed takes place in ductile fashion by means of at least one induction coil.
• an induction coil is to understand any device that can cause inductive heating.
• a single induction loop, for example, should also be understood as an induction coil.
• the procedure according to the invention has proven to be very particularly suitable for those cases in which the additional heating takes place inductively.
• the additional heating takes place inductively.
• for Erracer tion by means of one or more induction coils Wirbelströ me especially in a location under the location, already produced component section and / or located under a provided material layer work platform he testifies.
• heating usually takes place indirectly above the inductively heated solid bodies below, since an induction of eddy currents in the powder particles is generally negligible due to the small size of the particles.
• the taking place in the context of the inventive method to additional heating of an already manufactured Bauteilab section and / or a work platform on which the component is constructed, and / or each provided material layer can also be done simultaneously to the scanning process of the material layer with the at least one energy beam and / or this upstream and / or downstream.
• each of the material layers required for the production of a component of the desired geometry requires additional heating before and / or after and / or simultaneously or only for a part of the material layers.
• Detection means are provided for the metrological detection of the temperature distribution on the surface of the working platform and / or a component section already produced above the working platform and / or a material layer provided on the working platform or an already manufactured construction section;
• Control means which are adapted and arranged to vary the amount of energy introduced during a scan with at least one provided by the energy beam device energy amount depending on detected with the detection means temperature distribution, in particular such that a Inhomogeni ity of the temperature distribution is compensated or reduced.
• the detection means may in particular comprise or be given by at least one thermal camera.
• the means for heating may comprise at least one induction coil or be formed by a sol chen.
• control means of the device according to the invention are fer ner preferably designed and set up to carry out the method according to the invention described above.
• the control means may be constituted by or comprise a computer. They are in particular connected to the energy beam direction on the one hand and the detection means for metrological detection of the temperature distribution on the other hand, so that the measurement result can be passed to the temperature of a material layer provided to it and possibly evaluated, and at least one of the energy Beam direction provided energy, in particular laser beam is then controlled based on the result. So that an evaluation of the measurement result for temperature distribution can take place, the control means are preferably designed as control and evaluation means or else evaluation means are provided and connected to the control means.
• Another object of the invention is a component, in particular for a turbomachine, which was prepared by carrying out the method according to the invention.
• Figure 1 is a purely schematic perspective view of egg ner device for additive manufacturing of a construction part according to an embodiment of the present invention
• Figure 2 is a purely schematic sectional view of the device before direction of Figure 1;
• FIG. 3 shows a graph in which the temperature profile along a predetermined line is represented by a temperature image of the surface of a component section already provided by means of the thermal camera of the device of FIG. and
• Figure 4 is a graph in which a the temperature profile
• FIGS. 1 and 2 show purely schematic and highly simplified representations of an exemplary embodiment of an embodiment of the invention.
• inventive device for the additive production of a component of which in the figures an already manufactured component section 1 can be seen.
• FIG. 1 shows a perspective view
• FIG. 2 shows a sectional view. It should be noted that in both figures, components of the device are not shown, but which can be taken from the respective other figure.
• the device comprises, as previously known from the prior art, a defined by a cylinder 2 working space 3, in which a working platform 4 is arranged vertically movable over a punch 5. Cylinder 2, Ar beitsraum 3 and 5 stamp are only in the figure 2 Darge presents.
• the device further comprises means for providing a plurality of superimposed powder layers, which also in the prior art also known manner, not shown in the figures, directly adjacent to the cylinder 2 arranged powder reservoir and also not he detectable squeegee.
• the cylinder 2 is filled with powder 6.
• powder 6 from the powder reservoir is in each case conveyed in a sufficiently well-known manner into the working space 3 and smoothed out there.
• each of the powder layers provided on top of each other is selectively melted by means of a laser beam 7 in accordance with a predetermined component geometry.
• the laser beam 7 is provided by a set only in the figure 1 Darge laser beam device 8 of the device sheerge and by means of a scanning device 9 this process according to the predetermined geometry on the powder layer.
• the device further comprises means for inductive heating of the working platform 4 or on this be already constructed component section 1, which are presently given by an induction coil 10. With the help of the coil 10 eddy currents are induced during operation during a manufacturing process in the working platform 4 and / or on this already herge imputed component section 1 and this inductively heated. In particular, the formation of hot cracks is avoided or reduced by the additional inductive heating and it is also difficult to weld materials can be processed.
• a nickel base material is used.
• detection means for measuring technical temperature distribution on the upper surface of the working platform 4 or one above this be prepared already manufactured component section 1 and on the Oberflä surface of a provided powder layer are formed.
• the detection means are provided by a thermal imaging camera 11, which can only be seen in FIG. 1, of the apparatus which "looks at” from above in the direction of the work platform 4 or a substructure 1 already constructed thereon (see FIG. ,
• a further component of the device described here is a central control device 12, which with the punch 5, the means for providing powder layers, the laser beam device 8, the scanning device 9, the coil 10 and the thermal imaging camera 11 or a respectively associated further, Connected in the figures unrecognizable control device.
• the temperature distribution at that surface is measured detected, on which the respective powder layer is provided.
• the metrological detection of the temperature distribution is carried out in each case before the provision of the situation by a Tempe is taken raturstory of the respective loading riding surface with the thermal imaging camera 11.
• the detection and / or the time Liche evaluation of a detected temperature image is done as in preferably in temporal proximity to the subsequent scan process with the at least one energy, in particular La serstrahl.
• the thermal imaging camera continuously records and then the tempera tures of appropriate times are used.
• the thermal imaging camera 11 takes in a conventional manner, an image of the radiated from the respective surface heat mestrahlung in the infrared wavelength range.
• the surface temperature images obtained are in the form of temperature values for each camera pixel and can be used for further processing.
• the temperatures can be displayed, for example, in the form of false color or grayscale images.
• the first, lowermost layer is the surface of the working platform 4 pointing upwards in the figures and, for all other layers, the surface of the side of the respectively already constructed component section 1 pointing upwards in FIG.
• the temperature image recorded in advance for each layer is evaluated in each case, with concrete along predetermined lines which correspond to later scan lines of the laser beam 7, long of which the laser beam 7 on the respective position is procedural Ren, in order to selectively melt this, the temperature gradient is determined.
• the laser beam 7 is moved in the x and y direction over the layers, which is indicated in the figure 1 with two orthogonal zuei nander oriented double arrows.
• the determined temperature profile 13 along a predetermined line is shown by a temperature image detected for a component section 1.
• the y-axis is marked with "T” for the temperature and the x-axis with "s" for the distance along the component. It can be seen that there is a not inconsiderable inhomogeneity in the temperature distribution along the considered line. Specifically, there is a significantly higher temperature in the edge region than in the middle, which is due to a before ferred heating of component edges in the context of inductive heating.
• the amount of energy introduced by the laser beam 7 is varied during the process along the scan lines as a function of the determined temperature gradient during the subsequent Scanvor, and the art that the existing inhomogeneity is reduced or compensated.
• this is realized by adjusting the power of the laser beam 7 during the process along the respective scan line.
• An exemplary course of the laser power 14, wel holes for the temperature profile 13 shown in Figure 3 is compensating, can be seen from Figure 4.
• the y-axis with "P" for the laser power and the x-axis in turn with "s" for the route along the construction part is called.
• control device 12 includes u.a. a computer.
• the laser power and the traversing speed of the laser beam 7 can be adjusted to compensate for the inhomogeneous temperature distribution. It is also possible to change the density of the scanli nien. An additional or alternative Anpas solution of further laser parameters is also conceivable, as long as this compensation of an existing inhomogeneity due to the additional inductive heating is possible. Also, it is of course possible that, alternatively or in addition to the inductive heating, a heating is carried out on ande re way, for example, a resistive He warming or heating by means of IR rays. LIST OF REFERENCE NUMBERS

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• Analytical Chemistry (AREA)
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• Plasma & Fusion (AREA)
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• 2017
  • 2017-12-18 DE DE102017130282.4A patent/DE102017130282A1/de not_active Withdrawn
• 2018
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  • 2018-11-21 WO PCT/EP2018/082124 patent/WO2019120847A1/de not_active Ceased
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