Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
  • B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
  • B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
  • B23K26/062—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam
  • B23K26/0622—Shaping the laser beam, e.g. by masks or multi-focusing by direct control of the laser beam by shaping pulses
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
  • B23K26/14—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
  • B23K26/142—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor for the removal of by-products
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
  • B23K26/16—Removal of by-products, e.g. particles or vapours produced during treatment of a workpiece
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
  • B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
  • B23K26/355—Texturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
  • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
  • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
  • B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
  • B23K26/3568—Modifying rugosity
  • B23K26/3584—Increasing rugosity, e.g. roughening
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
  • C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons

Definitions

• the invention relates to an object with a metal substrate and a channel in the metal substrate which is completely or partially open to the surface, the channel having a very specific geometry.
• the invention further relates to a method for producing an object according to the invention using pulsed laser radiation.
• the invention relates to the object with a metal substrate and a channel in the metal substrate produced or producible by the method according to the invention and the use of the object according to the invention.
• Structures of this type can be used for contact surfaces, for example seals or bearings in moving components, for receiving lubricants, lubricants or sealants which are successively released to the contact surface during operation. Structures of this type can also be used in the field of medical technology for equipping implant surfaces.
• BMPs bone morphogenetic protein
• cytostatics or organisms eg phages
• Such storable layers can be produced or deposited on metallic material surfaces by means of different methods.
• the shape and size of the structures and the thickness of the structured layer have a major influence on the absorption capacity and release rate of substances.
• Structured and storable surfaces on metallic materials can be introduced in the prior art by means of special rolling processes during the manufacturing process. Alternatively, they can subsequently be produced from the material itself by depositing a coating or by removing material or by structurally changing the boundary layer. Pore structures, which can be produced in different layer thicknesses and pore densities depending on the method, have proven to be well suited with regard to a high storage capacity.
• layers with a pore structure can be created by thermal spraying processes (e.g. flame or arc spraying). Depending on the coating material and parameters, layers with a porosity between 3% and 15% can be produced in this way (see Oerlikon Metco. Introduction to thermal spraying - 6th edition. July 2016). Other structural shapes cannot be created using thermal spray processes. Since these techniques typically lead to a significant thermal entry on the substrate, they are not suitable for temperature-sensitive materials.
• sol-gel process Another method is the sol-gel process.
• immersion sols can be generated which have a porous layer on the substrate with a porosity of 50% to 85% (cf. Heidenau, Frank, et al. , et al. Open-pore, bioactive surface coatings on titanium. Biomaterials. 2001, Vol. 2, 1.).
• a general limitation with coatings is that there must be a good layer connection to the material, especially with mechanical loads.
• structures that are produced directly from the base material prove to be advantageous.
• different materials can be used.
• MAO Microarc Oxidation
• PEO Plasma Electrolytic Oxidation
• oxide layers are built up on metallic surfaces, for example titanium or titanium alloys.
• a suitable choice of process parameters can be used to create pore structures with a pronounced aspect ratio.
• a disadvantage of this process are the chemicals that are necessary depending on the metal and are sometimes extremely hazardous to health.
• the anodizing process is also known for aluminum or aluminum alloys.
• the uppermost metal layers are converted into an open-pored oxide or hydroxide by electrolytic oxidation.
• the pores can be closed by subsequent compression, for example in hot steam or water.
• the application of the anodizing process is limited to aluminum.
• Laser processes have also become established for the local structuring of metallic surfaces, in particular using ultrashort pulse lasers in the femto or picosecond range.
• the technology enables material to be removed without significant temperature introduction into the base material.
• US2008216926 describes the generation of nanostructures by means of a femtosecond laser.
• a nanostructured surface proves to be insufficient for the storage and release of substances or active ingredients.
• W010130528 describes the production of microstructures by repeated treatment with a pulsed laser in the picosecond range.
• the method enables the creation of pores with reduced pore opening diameters (“keyholes”) or with partial overhangs at the pore opening. Structures of this type can be used for medical implants (improved growth behavior and strength) or for mechanical clamping in adhesive bonds.
• US2016059353 describes a method for producing micro pores by a
• Laser treatment below the material-specific ablation threshold (necessary Energy density for material removal). The laser treatment continues until the pore structure is created (more than 1000 times or 2000 times). This type of process control leads to a low area coverage of the treatment. There is no specific definition of a laser type. However, treatment below the ablation threshold means that only poorly developed structures with small structural depths can form (lack of material removal). Accordingly, they have only a low storage capacity for liquid or pasty media.
• CN105798454 describes a structure for the treatment of surfaces with nanosecond lasers for the generation of cracks in the area near the surface.
• the documents in the laser area described above relate mainly to lasers with ultra-short pulses in the pico or femtosecond range. These systems can be used for the generation of defined structures without any significant thermal input to the surrounding material. Disadvantages are the comparatively high investment costs and the low realizable area rate.
• layers that are close to the surface and highly structured, which were produced from a metallic base material typically have only a low mechanical resistance.
• the object of the invention is achieved by an object with a channel in the metal substrate which is completely or partially open to the surface, the cross section of the channel having a local maximum width (5) between the channel bottom (7) and the contact plane (1) , measured perpendicular to the surface parallel to the plane of contact and perpendicular to the longitudinal axis of the channel, and in the area of the surface of the channel there is a heat-affected zone which has a grain size structure that is different from that of the metal substrate.
• the metal substrate is provided on at least one surface, it is preferred that the object itself predominantly or is made entirely of metal.
• the special geometry of the channel provided according to the invention indicates the specific manufacturing process on the one hand, and on the other hand enables a large number of applications.
• the contact plane is defined in particular in cross-section (section preparation) as follows: If there is a channel opening at the location to be examined, a circle with a radius of 3 mm is graphically inserted over this channel opening so that this circle is exactly 2 times ( once on each side of the channel) touches the proposed substrate. This situation is shown schematically on the right in FIG. 1b. The secant running through these two points of contact then represents the plane of contact.
• a “heat affected zone” in the sense of this text is an area that differs materially from the material of the substrate, the difference being able to be generated by heat treatment of the substrate or, preferably, actually being generated.
• a heat-affected zone in the sense of this text is characterized by a structure which is different from that of the metal substrate.
• a changed grain size structure means that there is a changed mean statistical grain size in the heat affected zone compared to the grain size of the metal substrate (without heat influence).
• the channel is closed in the cross-section, it may be that two positions are generally conceivable for the circle with a 3 mm radius (cf. left-hand side of FIG. 1 b).
• the secant is decisive for the definition of the contact plane, which under the aforementioned conditions intersects the associated circle with a radius of 3mm so that the longer distance is within the circle.
• the longitudinal channel axis in the sense of the present invention is the line which, in case of doubt, results from the channel bottoms of a plurality of cuts which, in case of doubt, are each made perpendicular to the longitudinal channel axis at a distance of ⁇ one tenth of the maximum width of the channel.
• the specific geometry of the channel in the subject matter according to the invention is accessible via a novel manufacturing method according to the invention (see below). Basically, this is treatment with pulsed laser radiation, the pulses hitting the same point on the metal substrate several times. Further details are given below in the context of the present description.
• the channels along the longitudinal axis of the channel can be designed in a variety of ways; it is possible to design straight lines and several channels in parallel, which is preferred in many cases. However, it is also possible to design the channel to be provided according to the invention in a meandering line or to provide a large number of channels which, for example, can also have crossings.
• 1 a schematically shows a cross section through the metal substrate, a channel being hit in the middle, which is closed at the level of the cut, while the channel is open on the right at the level of the cut.
• FIG. 1 b schematically represents FIG. 1 a, the circle having a radius of 3 mm for defining the contact plane being shown in each case.
• FIG. 2 schematically shows a parallel section to the substrate surface and shows a meandering channel on the left, parallel channels in the middle and crossing channels on the right, each schematically.
• FIG. 3 is again a schematic cross section through the metal substrate and shows channel structures which in principle consist of channels which merge into one another, but which are understood in the sense of the present invention as a channel in each case.
• 4 in turn shows schematically a cross section through the metal substrate in the region of a channel, the heat-affected zones which are brought about by the method according to the invention being drawn separately.
• an object according to the invention is preferred, the local width maximum (5) being> 0.5 gm below the contact plane (1).
• the channel having an aspect ratio of the local maximum width (5) perpendicular to the longitudinal axis of the channel measured to the channel length of> 1: 3, preferably> 1:10 and particularly preferably> 1: 100 and / or the channel a length of> 3 pm, preferably> 100 pm and particularly preferably> 500 pm, the channel length being measured in each case parallel to the object surface.
• the channel having a depth (3) of 0.1 pm to 10000 pm, preferably from 0.2 pm to 1000 pm and particularly preferably in the range from 0.5 pm to 500 pm perpendicular to the plane of contact (5.)
• the openings of the channel being from 0.05 pm to 2000 pm wide, measured in the contact plane (5), perpendicular to the longitudinal axis of the channel.
• An object according to the invention is preferred, the channel being covered to> 30%, preferably> 50% and in each case more preferably to> 70%,> 80%,> 90%,> 95% and> 99%, based on the the latitude maximum (5) spanned plane within the channel parallel to the contact plane.
• each channel has at least one opening to the surface.
• the channel is intended for purposes that essentially require the transport of material between two different locations, to configure the channel largely as a closed tube. In particular for such purposes, but also for purposes where a slow release of the channel content is desired, it is desirable that the channel is largely or completely covered.
• An object according to the invention is preferred with a first heat-affected zone in the opening area of the channel with an average statistical grain size smaller than the metal substrate in a ratio of min. 1: 2 particularly preferably min. 1:10 and a second heat-affected zone, which has a thickness of 0.1 pm to 3000 pm, preferably in the range of 0.2 pm to 1000 pm, particularly preferably in the range of 0, in the region of the lowest point of the duct or of the duct cross section.
• the second heat-affected zone perpendicular to the lowest point of the channel cross-section has an average statistical grain size smaller than the metal substrate of preferably ⁇ 1: 1, 2 and particularly preferably ⁇ 1: 5 and larger average statistical grain size compared to the first heat-affected zone of preferably> 2: 1, 2.
• the first heat-affected zone can be characterized by a martensitic structure, which is formed by rapid solidification after melting.
• the solidification rate must be at least 640 ° C / s for the formation of a martensitic structure. It can therefore be preferred to find a martensitic structure in the first heat-affected zone in the object according to the invention.
• This configuration of the heat-affected zones indicates on the one hand that the method according to the invention was used to produce the object according to the invention, and on the other hand there are various design options provided by the corresponding heat-affected zones: it is thus possible for the manhole cover to be designed from the area of the first heat affected zone, moreover, the heat-affected zones to be provided with particular preference according to the invention are particularly well suited to controlling the surface properties of the channel surfaces by a subsequent treatment.
• An object according to the invention is preferred, the metal substrate being selected from the group consisting of titanium, aluminum, vanadium, magnesium, copper, silver, lead, gold, their alloys with one another or with further metals and steel.
• an object according to the invention with an oxygen-enriched layer along the channel walls is preferred according to the invention, the oxygen enrichment measured to a depth of 50 nm, preferably 500 nm min. Is 5%, measured by means of XPS after sputtering and / or with one compared to
• Substrate nitrogen-enriched layer along the channel walls the nitrogen enrichment measured to a depth of 50 nm, preferably 500 nm min. Is 5%, measured by means of XPS after sputtering.
• the enrichment of oxygen or nitrogen indicates that the method according to the invention was carried out (although in case of doubt it was carried out under an oxygen atmosphere or nitrogen-enriched atmosphere, depending on which of the two elements was enriched against the substrate) on the other hand, the elemental composition of the channel surface, which has been changed in addition to the grain size, also offers further approaches for subsequent treatments, e.g. B. to adjust the surface property.
• the object according to the invention has an (enveloping) boundary layer around the channel, which has a depth of> 50 mm, preferably> 500 mm, in which the oxygen concentration> 0.5 atom%, preferably> 5 Atom% is and / or the nitrogen concentration is> 0.5 atom%, preferably> 5 atom%.
• the atomic% numbers given relate to the totality of all elements that can be detected with XPS.
• the XPS measurement is carried out with an upstream argon glove box for handling air-sensitive samples.
• the surface is removed e.g. B. via an argon ion sputter source. Sputtering continues until, according to the high-resolution spectra, the main element of the alloy (i.e. the element with the highest concentration in the alloy or in the case of a pure metal) is present in metallic elementary form (> 95 atomic%), the XPS measurement of the oxygen concentration or the nitrogen concentration at this point then preferably gives the values mentioned above .
• the object according to the invention preferably has specifically set properties in the region of the channel, in particular with regard to the surface energy or the wetting behavior.
• B. different channels have different surface properties such.
• the setting can be carried out, for example, using the following methods: CVD or PVD methods such as sputtering of titanium or deposition of plasma polymer layers in the PECVD method.
• the surface energies can preferably be set by means of plasma polymeric coatings in accordance with DE 102005052409 B3.
• the surfaces of the channel to be provided according to the invention preferably have a contact angle of ⁇ 60 °, at least locally, particularly preferably ⁇ 30 ° and very particularly preferably 0 °, in particular if the surfaces are intended to be hydrophilic, lipophilic or amphiphilic.
• Hydrophobic and lipophobic surfaces to be provided according to the invention preferably have a contact angle of> 90 °, particularly preferably> 120 °, the surface energy or the contact angle being measured by means of static contact angle measurement in accordance with DIN 55660-2: 2011-12.
• this object may be further optimize the surface properties of this object according to the invention for its desired purpose, in particular in the sense of the uses described as preferred here in this text.
• this coating now the ratio of the openings of the channel, measured in the plane of contact perpendicular to the longitudinal axis of the channel to the local maximum width between the channel floor and the plane of contact, is reduced by a maximum of 10% compared to a situation in which the additional coating would not be present.
• Part of the invention is also a method for producing an object according to the invention with a metal substrate, comprising the steps a) providing an object with a metal substrate and b) irradiating the metal substrate with a pulsed laser, the irradiation with at least 2 pulses, preferably at least 5 pulses, further preferably 2-2000 pulses, particularly preferably 5-100 pulses in a pulse repetition frequency of at least 0.1 kHz at the same point, the laser radiation used preferably having a wavelength in the range from 400 nm to 30 pm and preferably the pulse length for the Pulse is in the range 500 ps to 100 s.
• the laser treatment described in step b) has to be repeated several times, the site to be treated in each case preferably being at a defined distance from the site previously treated (unless it is the new beginning of a channel).
• the orientation of the individual points to each other defines the later channel orientation.
• the distance between the points can be described via the pulse overlap in the scan direction and depends on the spot diameter in focus (measurable according to the usual methods for laser technology).
• the spot diameter in focus is preferably -25% to 90% of the spot diameter in focus, particularly preferably 10% to 75% of the spot diameter in focus (negative information for the spot diameter describes two positions with an area in between, to which no laser power is incident).
• Channels lying in parallel are created by repeating this line treatment at a defined distance from the first channel. The distance of this line treatment depends on the desired density of the channels as well as the overlay and coverage of the individual channels.
• a method according to the invention is preferred, the laser radiation used having a wavelength in the range from 400 nm to 30 pm, preferably from 950 nm to 12 pm.
• a method according to the invention is also additionally preferred, the pulse repetition frequency being in the range from 0.1 kHz to 4 MHz, preferably in the range from 10 kHz to 250 kHz.
• the pulse length for the pulses is in the range 500 ps to 100 s, more preferably in the range 1 ns to 100 ps, particularly preferably in the range 5 ns to 10 ps. This has a positive influence on the fact that the desired structures arise in the method according to the invention.
• the energy density measured in the sample position by means of a pyroelectric sensor in the laser beam focus is 0.1 J / cm to 100 J / cm 2 , particularly preferably in the range 1 J / cm 2 to 20 J / cm 2 .
• the energy distribution in the laser spot has a Gauss profile or flat-top profile or top-hat profile.
• a method according to the invention is preferred, wherein the irradiation of the metal substrate in step b) is carried out with a CW or a QCW laser, the local duration of the laser pulse in a surface area corresponding to the spot size being at least 5 ns, preferably at least 25 ns, being further preferred in the range between 40 ns and 2 ms, particularly preferably 50 ns - 500 ns.
• step b) in the method according to the invention the laser is carried out in such a way that when step b) is repeated, the pores generated together result in a channel that is completely or partially open to the surface.
• the method according to the invention can in principle be used on all metallic materials as long as they form a melting phase under laser irradiation.
• the emitted wavelength of the laser source used is not restricted. However, this is preferably a wavelength and pulse duration which leads to a thermal interaction on the material. It is particularly preferred to use lasers in the near (fiber or Nd: YAG laser) or middle IR range (CO 2 laser) with pulse durations greater than or equal to the ns range (> 1 ns).
• the fluence striking the surface must be high enough to create a melting front.
• the pulse frequency must be selected in such a way that the time between two pulses is not sufficient to re-solidify the melting front.
• Part of the invention is also the use of an object according to the invention, the metal substrate provided with one or more channels being used as a storage view for active substances, preferably selected from the group of phages, antibiotics, virustatics, chemostatics, cytostatics, bioglass and / or as a storage layer for culture media for cells, preferably tricalcium phosphate, glucose, lipids, amino acids, proteins, minerals and / or as a habitat for cells, preferably human cells, preferably human stem cells and / or fungi and / or spores and / or bacteria and / or as a substrate to improve osseointegration, that is, the uptake of or the growth of osteoblasts.
• active substances preferably selected from the group of phages, antibiotics, virustatics, chemostatics, cytostatics, bioglass and / or as a storage layer for culture media for cells, preferably tricalcium phosphate, glucose, lipids, amino acids, proteins, minerals and / or
• An inventive use of the object according to the invention is also the use of the metal substrate provided with one or more channels as a storage layer for tribologically active substances, preferably those for friction reduction, such as, for example, lubricants, in particular oils, non-metallic particles, preferably particles of crystalline substances with the space group P63 / mmc (Space group No. 194), more preferably inorganic substances, more preferably from the group of graphites, molybdenum disulfides, tungsten disulfides, their intercalate compounds and / or for the absorption of oils, proteins, hormones and / or heavy metal ions.
• the object according to the invention can be used in the area of a heat exchanger.
• Part of the invention is also the use of an object according to the invention for the absorption and delayed release of liquids, gases and / or solids in or from the channel to be provided according to the invention.
• the absorption capacity of the channel according to the invention based on the channel base area, i.e. the local maximum width (5) of the channel multiplied by the channel length (6), is preferably> 0.0001 cnfVcm 2 , more preferably> 0.001 crrvVcm 2 , more preferably> 0.01 cnfVcm 2 , particularly preferably> 0.1 cm 3 / cm 2 .
• the volume measurement of the duct is determined by weighing the recorded material (differential weighing before and after the exposure).
• Part of the invention is also the use of the object according to the invention for the transport of liquids, dispersions and / or gases through the channels.
• This is possible, for example, in that the object according to the invention is partially immersed in a liquid, such as water, and the corresponding liquid emerges at the end of the channels.
• Example 1 Section preparation on a laser-induced channel structure on a Ti6AI4V
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany with stamp optics and f (330) f-theta lens)
• Pulse repetition frequency 200 kHz
• FIGS. 5 a) and b) show a microscopic characterization of a cut in the X direction, that is perpendicular to the direction of travel of the laser of the surface-modified substrate produced in Example 1.
• the reference symbols mean
• the section preparation perpendicular to the channel direction shows channels that are closed locally at the location of the section (A), as well as channels that are covered upwards (B) or have a keyhole-shaped opening (C) .
• These structural forms oscillate along the channels in the process parameter used.
• the edge zones of the channels have a grain size distribution that is different from the basic structure (bulk material) of the metal alloy.
• At the bottom of the channel there is only a phase of the finest grain size distribution (1), including two further phases with an increasing coarsening of the grain size distribution (2) and (3). This is characteristic of the invented laser process according to the invention in the case of a treatment in particular on ⁇ 6AI4L / and the structures thus formed on this material.
• the section preparation parallel to the channel direction shows a channel that is completely continuous in the visible sample area with covered partial areas (B) and open partial areas (C).
• Example 2 Chemical composition of the laser interaction zones and the unaffected bulk (corresponding to Example 1)
• the modified substrate produced according to Example 1 was further characterized after grinding preparation as in Example 1 by means of energy dispersive X-ray spectroscopy (EDX). There are no large-scale differences in the element concentrations of titanium, aluminum and vanadium within the resolution limit (approx. 1 pm) in the heat-affected areas.
• EDX energy dispersive X-ray spectroscopy
• Example 3 Treatment of a round wire surface and influence of the laser settings
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany with stamp optics and f (330) and f (160) f-theta lens)
• the Ti6AI4V surfaces on round wires produced with the process parameters described have parallel channel structures analogous to the observations in Example 1.
• the structure sizes such as the pore depth and width as well as the opening diameter decrease with the use of a smaller focus diameter (parameter L17 compared to parameter L2).
• Example 4 Loading of the porous surfaces Process conditions / parameters: Material: 2 cm x 2 cm Ti6AI4V flat substrate
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany with stamp optics and f (330) and f (160) f-theta lens)
• Preparation A drop of approx. 10 pl water was pipetted onto the samples, then the surface was dried with a lint-free cloth. For this purpose, a 4-fold Kimwipe cloth (Kimberly Clark 7552, Kirnte ch Science precision cloths) was pressed onto the surface for 5 seconds, after which this was repeated with a new Kimwipe cloth. The mass increase of the samples was then determined using a fine balance.
• the surface energy can be specifically adjusted by coatings, e.g. also locally, for example inside and outside the pores or channels.
• a titanium dioxide layer (T1O2) is deposited by reactive sputtering of metallic titanium.
• the low-pressure reactor is evacuated to a base pressure of 1 * 10 5 mbar using a turbo drag pump (520 l / s).
• argon is introduced into the reactor at a flow of 120 sccm, so that a pressure of 5 * 10 3 mbar is established in the reactor.
• a high-frequency plasma power (13.56 MHz) of 2400 W is coupled in for free sputtering of the titanium target.
• the magnetron itself is flanged to the reactor. After about a minute of free sputtering, an additional 9 sccm of oxygen is let into the reactor.
• FIG. 7 shows the transmission as a function of the substrate-titanium target distance. At a distance of 470 mm, there is a clear deviation from the calculated transmission of pure T1O2 because the titanium has not been completely oxidized to T1O2. If the distance is increased to 565 mm, almost pure T1O2 is deposited on the substrate.
• Example 6 Improvement of the biocompatibility
• the improvement of the biocompatible properties of the object according to the invention is possible through a subsequent coating with metallic titanium. If necessary, existing, toxic nanoparticles are bound by the titanium layer or the changed roughness of the surface has a positive effect.
• Titanium Titanium is deposited by non-reactive sputtering in an argon atmosphere.
• the 50 x 50 x 50 cm reaction chamber vacuum chamber
• 120 sccm argon is let into the reactor.
• the pressure rises to 5 10 3 mbar.
• 2400 W is selected as the sputtering power.
• the distance between the titanium target and the substrate is 20 cm.
• an approximately 100 nm thick titanium layer has grown on the substrate.
• the layer thickness can be determined using transmission spectroscopy if the calculated transmission spectrum of a Ti layer matches the experimental spectrum.
• the metal substrate from Example 1 to be used according to the invention which also has many nanoparticles on the surface, the biocompatibility can be improved. This is attributed to the special procedure of laser treatment, whereby the nanoparticles are firmly attached and the titanium layer has good adhesion.
• Example 7 Steel treatment
• Example 8 Steel as a substrate
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany with stamp optics and f (330) and f (160) f-theta lens)
• the structures (channels) to be provided according to the invention are reliably produced on steel surfaces. Depending on the laser fluence, different dimensions arise with regard to the pore depth and width, the opening diameter and the heat affected zone.
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany with stamp optics and f (330) f-theta lens)
• Pulse sequence frequency 150 kHz
• the parallel channels have a minimum depth of (100 +/- 40) pm, a width of (75 +/- 25) pm, and a length of 10 cm.
• the channels are partially open, with the opening width varying between less than 1 pm and 70 +/- 20 pm.
• Example 10 Overlapping channels A higher line overlap in the laser scanning process (e.g. 75%) creates parallel channels with an overlapping cross-section:
• Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany with stamp optics and f (330) f-theta lens)
• Emitted wavelength 1064 nm
• Pulse repetition frequency 100 kHz pulse length: 129 ns
• Laser fluence on the substrate 10.5 J / cm 2
• the parallel channels have a minimum depth of (400 + - 50) pm, a width of (250 + -100) pm, and a length of more than 10 cm.
• the channels are partially covered.
• Example 11 Grain size distribution The different grain size distributions in the first heat affected zone, in the present example with an extension from the contact plane 150 pm +/- 50 pm, the second heat affected zone, in the present example with an extension of 25 pm, and the substrate was subsequently examined ( as a result of sample preparation as in Example 1; see FIG. 5 a) and b)): Material: Ti6AI4V flat substrate
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany with stamp optics and f (330) f-theta lens)
• Target power 100% (100 W) Pulse repetition frequency: 200 kHz
• FIB preparation Fecused Ion Beam; device: Helios 600, FEI; manufacturer: FEI, Hillsboro, Oregon, USA
• STEM scanning transmission electron microscope
• Tecnai TF-20 S-Twin G 2 manufacturer: FEI, Hillsboro, Oregon, USA
• determination of the mean diameter of the grains by determining the mean grain diameter in the center of gravity of the grains.
• An anti-bacterial coating should be developed that has a high absorption capacity for various active ingredients.
• the active ingredient is said to be simple Immersing the coated implant in a drug solution.
• the release of the loaded coating should be in the range of 30 minutes. It is crucial, however, that the material is dispensed in large doses immediately after the implant is inserted.
• Various approaches for storage layers with a release function are known from the literature. The special focus here is on titanium dioxide nanotubes, which can be produced by simple anodization and which provide a large reservoir for materials. However, the long loading times are a disadvantage. Depending on the exact type of nanotube, up to five loading cycles per hour are required. Requirement profile:
• the 2x2 cm 2 large laser-structured sample [from which example?] Is immersed in a concentrated methylene blue solution (30 mg / ml) for 5 min. Then the back and the four edges are wiped with a paper towel. The sample surface itself is dabbed with a paper towel until no further dye emerges from the surface.
• XPS X-ray photoelectron spectroscopy
• Ti6AI4V flat substrate (supplier: Rocholl GmbH, Aglasterhausen, Germany)
• the XPS investigations were carried out with a Thermo K-Alpha K1102 system with an upstream argon glovebox for handling air-sensitive samples.
• CAE Constant Analyzer Energy-Mode
• the XPS measurements show a cleaning of the Ti6AI4V by laser treatment. Both the carbon content is reduced and the small amounts of Si, Mg, Ca, Zn and S are removed. You can also see an increase in the proportion of oxygen on the surface (formation of titanium oxide).
• a Ti6AI4V surface should be generated on a K-Wire, which has a good cell growth and cell growth behavior.
• a channel structure according to the invention was generated using laser technology and the surface was provided with a sputter layer made of titanium dioxide.
• the latter can (generally preferred according to the invention) contain firmly embedded silver particles in order to achieve an additional antibacterial effect.
• the cell behavior is checked with MG-63 osteoblasts, followed by a preparation of the cell-covered surface for characterization in a raster re-electron microscope.
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany with stamp optics and f (330) f-theta lens).
• the laser treatment was carried out with the parameter L2 from Table 6.
• the wire was rotated in three steps by 120 ° under the laser and the top surface was treated with the laser.
• the scanning direction was perpendicular to the longitudinal direction of the wire.
• the titanium dioxide layer (T1O2) is deposited by reactive sputtering of metallic titanium.
• a low-pressure reactor with a volume of 125 l is evacuated to a base pressure of 1 10 5 mbar using a turbo drag pump (520 l / s). Then argon is introduced into the reactor at a flow of 120 sccm, so that a pressure of 8 10 3 mbar is established in the reactor.
• a high-frequency plasma power (13.56 MHz) of 2400 W is coupled in for free sputtering of the titanium target.
• the magnetron itself is flanged to the reactor.
• lent 9 sccm oxygen to the reactor. This low oxygen flow ensures that the 250 mm round target is not poisoned and that titanium oxide is deposited on the substrate.
• an approximately 30 nm thick TiCfe layer is deposited on the substrate.
• Ethanol treatment The cells were treated with increasing ethanol concentration. The cells were incubated for 10 min each with 30%, 50%, 70%, 80%, 90%, and 2 x 100% ethanol (in ddH20, v / v) at room temperature (RT).
• HMDS hexamethyldisilazane
• the biocompatibility of the coating enables osteoblasts to adhere to the surface and to colonize it.
• the SEM picture of the treated surface shows a successful colonization with osteoblasts.
• a large number of osteoblasts can be seen above, between and in the raised areas of the laser structure, which spread over the surface and grow into the recesses and also partially cover them.
• the dense cell network formed suggests a high affinity of the cells for adherence and proliferation on the surface, as well as their characteristic, spreading shape for a good vitality of the osteoblasts. This cell growth and cell growth behavior is seen as the basis for stable osseointegration.
• FIG 10 shows SEM images of osteoblasts on bright-rolled titanium surfaces according to the invention at different times.
• the cells After thirty minutes of incubation, the cells initially show a spherical shape and individual philosophies from the cell mass center of gravity towards the surface. After four hours of incubation, the philosophies point in all directions. The cells bridge the trenches on the surface according to the invention. After a few days, the growth of the philosophies in the undercut trench structures can be observed. The cells appear flat on the bare reference sheets, but without the possibility of migrating into the structures of the material.
• the laser structures according to the invention with and without additional titanium dioxide coating show no optical differences in the morphology of the colonizing cells.
• a preferred use of the substrate according to the invention is use as an implant, particularly preferably after coating with a coating which improves the biocompatibility, in particular with titanium dioxide.
• Example 15 Bonding Lasered and non-lasered stainless steel samples (AISI 316L; WNr. 1 .4404) are bonded and the bond is tested using a tensile shear test. The influence of a laser-induced trench structure on the strength of the bond is checked. Used material:
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany
• stamp optics and f (330) f-theta lens.
• the laser optics and the samples to be treated were in a laser protection cell (aluminum) with suction. To avoid particle redeposition, the samples were also flushed with a compressed air stream of 45 N l / min (inlet pressure 8 bar; 20 ° C) using a compressed air nozzle (mounted at an angle of 45 °; directed directly at the samples) during the laser treatment.
• Adhesive surface approx.12.5 mm x 25 mm
• the adhesive was applied to one of the two sheets.
• the second sample sheet was then placed on top and the bonded area was loaded with a pressure weight of 500 g.
• washers of a suitable size were pushed under the upper sample. After curing, the samples were tested according to the specifications in DIN EN 1465:
• Test system Zwick BT1-FB020TN.D30
• Untreated and wet-chemically pretreated (treatment in an ultrasonic bath, 10 min, room temperature, isopropanol / water mixture in a volume ratio of 9: 1) served as references.
• 5 untreated, 5 wet-treated, 5 treated with L1 and 5 treated with L5 test specimens were produced in this way.
• a significantly increased tensile shear strength can be seen through the laser treatment (with both L1 and L5) compared to the untreated or wet-chemically pretreated samples.
• the untreated and wet-chemically pretreated test specimens show a completely adhesive adhesive failure at the interface with the steel.
• the laser-treated samples fail completely cohesively in the adhesive. From this it can be deduced that the inventive use of the substrates according to the invention serves to improve the bondability compared to untreated substrates.
• Example 16 Filling the structures with tricalcium phosphate (TCP)
• TCP is metabolized by living cells and therefore serves as a nutrient medium and to improve cell growth behavior on surfaces.
• a prerequisite for use in the medical field is a good connection of the TCP layer on the respective surface. With rough surface structures there is also the possibility of tissue ingrowth in the TCP-filled cavities.
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany
• stamp optics and f (330) f-theta lens.
• the laser optics and the samples to be treated were in a laser protection cell (aluminum) with suction. To avoid particle redeposition, the samples were also laser-treated with a compressed air nozzle (mounted at an angle of 45 °; directed directly at the samples) with a compressed air flow of 45.7 N l / min (inlet pressure 8 bar; 20 ° C) washed around.
• Table 9 Laser parameters for the fixation of tricalcium phosphate
• the parameter corresponds to the laser parameter L1 from Example 15.
• the microscopic image shows the undercut trench structure according to the invention.
• TCP CA-PAT-01-NP (American Elements, Los Angeles, USA).
• Preparation of the suspension After adding the TCP to the ethanol, the suspension is mixed for 10 minutes using a magnetic stirrer (at room temperature) and then placed in an enclosed beaker for 10 minutes at room temperature in an ultrasonic bath. The surface structure is filled using the dipping process as soon as possible after the ultrasonic bath (type Ultrasonic 300TH, VWR) to avoid reagglomeration or sedimentation of the nanoparticles. Filling: The freshly mixed suspensions are placed in a flat glass bowl. Sufficient of the suspension must be filled in so that the sample is completely covered with it. The samples are then added to the suspension with tweezers and left there for 30 s. They are also removed using tweezers. During the entire process, the samples must be in one horizontal position.
• the samples are dried in an air atmosphere for 10 min.
• a sintering process is carried out in a protective gas atmosphere (argon) in a high-temperature furnace (model 16-6, H. Dieckmann).
• the sintering process takes place with a heating and cooling rate of 30 K / min and a holding of the final temperature at 1050 ° C for 1 minute.
• FIG. 12 shows the area-specific mass change in relation to the mass of the lasered or unlasered and unfilled surface.
• Superhydrophobic surfaces are used, for example, to achieve an easy-to-clean effect.
• a micro- and / or nanostructured topography is characteristic of such a surface.
• a possible way of realizing such a surface is a thin, plasma-polymeric coating which, with a suitable choice of the process parameters, leads to a structured surface. Due to the extremely fine structures, superhydrophobic surfaces are generally sensitive to abrasion. It is checked to what extent these properties can be stabilized by applying them to a surface macroscopically structured by laser.
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany
• stamp optics and f (330) f-theta lens.
• the laser optics and the samples to be treated were in a laser protection cell (aluminum) with suction.
• the samples were also laser-treated with a compressed air nozzle (mounted at an angle of 45 °; directed directly at the samples) with a compressed air flow of 45.7 N l / min (inlet pressure 8 bar; 20 ° C) washed around.
• FIG. 13 shows microscopic images of the surface structure produced in this way.
• 13 shows microscopic images of a surface structure produced by means of L14 (left) in plan view and (right) in the side layer.
• Plasma source PFW10 (manufacturer Plasmatreat, Steinhagen)
• HTR12 manufactured by Plasmatreat, Steinhagen
• Nozzle head attachment IFAM type 21837 (W020000EP02401) (for step 1 and step
• the samples were stored at room temperature for at least 6 h before further testing was carried out.
• the abrasion resistance was tested using a measuring system from TQC (type: Abrasion Tester). A stamp with a test cloth attached to it was rubbed over the surface at a defined load and speed. The test was carried out using the following parameters.
• Test medium ISO Cracking Cloth (manufacturer: James Heal; according to ISO 105-F09) Weight: 500g
• Dataphysics OCA 50 a fully automatic contact angle measuring device with contour analysis system based on DIN 55660-2. 6 pl water drops with a volume flow of 12 ml / min were applied, and the advancing contact angle was measured.
• a non-undercut laser structure in combination with an identical plasma coating already shows a contact angle of 137 ° after 10 cycles of abrasion (with an initial value without abrasion of 150 °).
• the coating on an undercut laser structure according to the invention therefore has a higher stability to abrasion than a non-undercut structure.
• a substrate according to the invention for stabilizing coatings or their properties applied thereon, compared to a substrate which does not have the structuring according to the invention.
• the development goal is to produce biocompatible, laser-structured titanium and stainless steel surfaces that can be equipped with vital, metabolically active cells in order to create a functionalization of the biological / technical system that would not be possible with the organism or the material alone .
• the biological material should be introduced by inoculation with a suspension of cells and nutrient solution and takes place through the capillary effect. Subsequent cell growth ensures that the cells spread throughout the capillary system of the laser-structured materials and on the surface.
• the settlement in the capillary system protects the cells from mechanical abrasion, so that the system can regenerate in such cases and can generate a biofilm / mycelium on the surface again.
• the biofilm / mycelium makes the raw materials hydrophobic and creates a stable lubricating film on the surface under atmospheric conditions. Genetic changes in the bacterium used ensure fluorescence of vital cells so that process monitoring can take place.
• Titan Ti6AI4V, 1 mm thick sheet
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany
• the bacterium Pseudomonas fluorescens (DSM No. 50090) is used. It is a gram-negative, oxidase-positive, rod-shaped bacterium with a tuft of pinnacles. Furthermore, the application has been carried out with the anamorphic fungus Penicillium simplicissimum (DSM No. 1078).
• the vitality of the cells was demonstrated by a live dead staining (SYTO 9 dye and
• the large-scale spread of the organisms in the laser-structured habitat can also be detected and evaluated using the techniques mentioned.
• genetic engineering changes transformation according to Hanahan, 1983 and Mandel and Higa, 1970; CaCI2 method
• the 2x2 cm2 laser-structured sample is loaded with 150 pl of a solution of Pseudomonas fluorescens and LB medium [Carl Roth GmBH + Co. KG, Düsseldorf] [100 pl] / glucose [50 pl] mixture.
• the cell suspension is drawn into the channels via capillary forces.
• Penicillium simplicissimum loading is also carried out by applying 150 pl of a mixture of a stock solution with liquid potato extract-glucose broth [Carl Roth GmBH + Co. KG, Düsseldorf].
• the cell solution is automatically drawn into the cavities by the capillary effect.
• the hydrophobicity of the surface by the Pseudomonas fluorescens biofilm and the Penicillium simplicissimum mycelium was determined by contact angle measurements (Krüss DAS 100S) using the captive bubble / sessile bubble method. Under the fluorescence microscope, the advanced colonization of the laser-structured cavities by P. simplicissimum is clearly visible after 120 hours and after 24 hours of incubation. It can be seen that the fungus is already pulling through the substrate and is spreading beyond it. P. simplicissimum is therefore vital and able to fully colonize the laser-structured habitat.
• the contact angle measurements showed contact angles of 20 ( ⁇ 3 °) for the reference samples.
• the hydrophobicity is proportional to the biofilm / the spread of the fungal mycelium. Literature for this example
• Example 19 Aluminum-aluminum composite casting
• insert sheets to be cast on are therefore structured with an undercut channel structure according to the invention by means of laser technology, the infiltration of the melt into the channel structure achieving a positive connection between the aluminum insert component and the cast component.
• the maximum bond strength is determined by tensile shear tests.
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany
• the laser optics and the samples to be treated were in a laser protection cell (aluminum) with suction.
• the channel structure according to the invention is generated by the orthogonal superimposition of two trench structures.
• 75 gm-wide undercut trenches are first created perpendicular to the flow direction of the melt using parameter L13 (see FIG. 15 a). This is followed by structuring offset by 90 ° with parameter L14, which creates trenches 75 ⁇ m wide parallel to the flow direction of the melt (see FIG. 15 b). Due to the overlay, the upper trenches, which run parallel to the flow direction, are connected below by the previous structuring.
• FIG. 15 c) shows the orthogonal superposition of the structures from FIG. 15 a) and b).
• FIG. 15 shows microscopic and schematic representations of the channel structures on aluminum produced using laser technology (AIZnMgCul, 5).
• AIZnMgCul, 5 AIZnMgCul, 5
• a Structure with parameter L13 (perpendicular to the flow direction of the melt)
• b Structure with parameter L14 parallel to the flow direction of the melt).
• the aluminum insert sheets with the dimensions 39.9 mm x 99 mm x 1.5 mm were first structured along their full width and a height of 2 mm with parameter L13 perpendicular to the flow direction of the melt and then with parameter L14 parallel to the flow direction of the melt , so that the channel structure according to the invention is shown (see FIG. 15).
• the steel insert sheets with the dimensions 39.9 mm ⁇ 99 mm ⁇ 1.5 mm were initially structured along their full width and a height of 10 mm with the parameters L1s, L2s L13s and L22s, so that the channel structures according to the invention are reproduced.
• the structured insert sheets were cast on with the help of a cold chamber die casting system SC N 66 from the manufacturer Bühlers using a gate speed of 40 m / s and a holding pressure of 750 bar.
• the temperature of the aluminum melt was 740 ° C. After quenching, the samples were additionally aged for eight hours at a temperature of 170 ° C.
• the cast-on structured and blank insert sheets serving as reference samples were tested with a tensile shear test according to DIN EN 1465 on the Zwick-Roell test system Z020 and Z050.
• the test is carried out with a 20 kN or a 50 kN force transducer and a test speed of 10 m m / min.
• the tensile shear test consists of the insert plate (39.9 mm x 99 mm x 1.5 mm) and the cast component overlapping on one side (40 mm x 98 mm x 10 mm). The overlap is along the full width and over a length of 40 mm.
• Figure 16 shows tensile shear strengths of cast-on aluminum insert sheets with various pretreatments.
• FIG. 17 shows tensile shear strengths of cast-on steel insert sheets with various pretreatments.
• the channel structure c for single aluminum sheets which results from the orthogonal superimposition of the structures a and b, a significantly increased tensile shear strength can be achieved compared to the untreated or the corundum blasted samples.
• the pretreatment of the inserts by laser structuring enables the doubling of the Bond strength against materially bonded composites by means of pretreatment using the zincate process (according to Papis, K .; Hallstedt, B .; Löffler, J .; Uggowitzer, P .; Interface formation in aluminum-aluminum compound casting, Acta Materialia 56, 2008).
• the laser structures according to the invention with the laser parameter L13s in the cast aluminum composite show high strengths and low standard deviations with over 79 ⁇ 0.5 MPa.
• the result shows that the objects according to the invention can be used generally to improve the tensile shear strength for cohesive composites compared to substrates which do not have the structuring to be provided according to the invention. This applies in particular to cohesive connections which have been produced in the die casting process, but is not restricted to this.
• Example 20 Mass Transport ⁇ Microfluid Reactor Microflow reactors enable controlled chemical reactions on a submillimetre scale. They are characterized by good reaction kinetics and heat exchange coefficients.
• the undercut channel structures according to the invention can be used for such microreactors. This means that metallic surfaces can be equipped with micro reactors.
• 100W Nd YAG laser (type CL100 from CleanLaser, Herzogenrath, Germany
• stamp optics and f (330) f-theta lens.
• the laser optics and the samples to be treated were in a laser protection cell (aluminum) with suction. To avoid particle redeposition, the samples were also flushed with a compressed air stream of 45 N l / min (inlet pressure 8 bar; 20 ° C) using a compressed air nozzle (mounted at an angle of 45 °; directed directly at the samples) during the laser treatment.
• the undercut channels according to the invention were first lasered onto the sheet steel surface with the laser parameter LA in the form of two inflow zones A and A * . These inflow zones serve to introduce the reactants and are connected to one another via a reaction zone B.
• This reaction zone B was realized in that parallel undercut channels were lasered orthogonally in two cycles onto the surface with the laser parameter LB, so that the channels intersect.
• An outflow zone C for the reaction products was then lasered onto the surface by means of parallel channels onto the surface with the parameter LC, which is connected to the reaction zone B via the undercut channels. Proof of function:
• sodium hydroxide solution (2% by weight in water) and a fluoresceine / water / ethanol mixture in the ratio (0.1: 6: 24) were used as reactants. These reactants were pipetted onto one of the inflow zones A and A * with three 20 ml drops of the respective solutions.
• the detection of the reaction takes place on the basis of a fluorescence detection with a UV lamp, the initially colored form of the fluorescein being converted into a fluorescent molecule with sodium hydroxide solution with the elimination of water and sodium ions.
• a 4-fold collecting cloth (Kimberly Clark 7552, Kimtech Science precision towel) was used as a reservoir for the reaction products, which was pressed onto the surface of the discharge zone C.
• the reactants initially wet the channels of the inflow zones A and A * within one second, which can be observed from the channel openings.
• FIG. 19 documents the visible fluorescence through the channel openings in reaction zone B after about two seconds. This is the proof of the reaction of the two reactant solutions which mix in reaction zone B.
• the fluorescent lighting can be seen in the form of a volume flow along a reaction zone. After about four seconds, the reaction products reach the collecting cloth, which also fluoresces. (The time was measured using a video documentation of the experiment)

Landscapes

• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Mechanical Engineering (AREA)
• Plasma & Fusion (AREA)
• Chemical & Material Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Laser Beam Processing (AREA)
• Materials For Medical Uses (AREA)
• Other Surface Treatments For Metallic Materials (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=69156381

Family Applications (1)

Country Status (7)

Families Citing this family (6)

Family Cites Families (20)

• 2018
  • 2018-12-21 DE DE102018133553.9A patent/DE102018133553A1/de active Pending
• 2019
  • 2019-12-18 CN CN201980085295.8A patent/CN113226625A/zh active Pending
  • 2019-12-18 JP JP2021536355A patent/JP7550763B2/ja active Active
  • 2019-12-18 BR BR112021012060-2A patent/BR112021012060A2/pt unknown
  • 2019-12-18 WO PCT/EP2019/086112 patent/WO2020127594A1/de unknown
  • 2019-12-18 EP EP19835281.7A patent/EP3898066A1/de active Pending
  • 2019-12-18 US US17/311,981 patent/US20220048133A1/en active Pending

Also Published As

Similar Documents

Legal Events