EP4118042A1 - Procédé de production de buses pour fibre de verre et buse pour fibre de verre - Google Patents

Procédé de production de buses pour fibre de verre et buse pour fibre de verre

Info

Publication number
EP4118042A1
EP4118042A1 EP21705920.3A EP21705920A EP4118042A1 EP 4118042 A1 EP4118042 A1 EP 4118042A1 EP 21705920 A EP21705920 A EP 21705920A EP 4118042 A1 EP4118042 A1 EP 4118042A1
Authority
EP
European Patent Office
Prior art keywords
base plate
tube
passage
glass
tubes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21705920.3A
Other languages
German (de)
English (en)
Inventor
Sascha SAGER
Jakob Fischer
Stephan Herbst
Stefan Lang
Lisa Meyer
Stefan Vorberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heraeus Deutschland GmbH and Co KG
Original Assignee
Heraeus Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Heraeus Deutschland GmbH and Co KG filed Critical Heraeus Deutschland GmbH and Co KG
Publication of EP4118042A1 publication Critical patent/EP4118042A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/08—Bushings, e.g. construction, bushing reinforcement means; Spinnerettes; Nozzles; Nozzle plates
    • C03B37/083—Nozzles; Bushing nozzle plates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/08—Bushings, e.g. construction, bushing reinforcement means; Spinnerettes; Nozzles; Nozzle plates
    • C03B37/0805—Manufacturing, repairing, or other treatment of bushings, nozzles or bushing nozzle plates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/08—Bushings, e.g. construction, bushing reinforcement means; Spinnerettes; Nozzles; Nozzle plates
    • C03B37/095—Use of materials therefor

Definitions

  • the invention relates to a method for producing glass fiber nozzles.
  • the invention also relates to a glass fiber nozzle and a method for producing glass fibers.
  • Glass fiber nozzles for drawing technical glass fibers can be produced by flowing a glass melt through openings in a base plate of a glass tank.
  • a glass fiber nozzle can be welded together from a box-shaped structure with a perforated base plate, with tubes or so-called tips with a cylindrical or conical shape being welded into the holes in the base plate.
  • Certain tube geometries are advantageous here, but in some cases can only be produced with great effort using conventional methods.
  • the glass fiber nozzles are equipped with up to 8,000 tubes (tips). The liquid glass (or the glass melt) runs out through the glass fiber nozzle through these tubes. The cooling of the glass creates solid glass fibers.
  • the tubes have a significant influence on the quality of the glass fibers as well as on the service life of the glass fiber nozzle.
  • US 2016/0312338 A1 discloses a glass fiber nozzle made of a platinum-rhodium alloy, in which a multiplicity of tips are arranged on one side of a base plate (“bushing”).
  • the tips are arranged in a large number of passages through the base plate and extend it.
  • the glass melt can flow out through the passages and the tips for the production of glass fibers.
  • the tips are either welded on or they are made in one piece with the base plate and together with the base plate.
  • the tips should be made of the same material as the base plate.
  • a one-piece production of the base plate with the tips and the passages is complex.
  • the base plate cannot be rolled in such a production in order to achieve stiffening and an improvement in the durability of the base plate.
  • the welded connection represents a weak point in the glass fiber nozzle.
  • all tips have to be laboriously welded individually to the base plate.
  • unwanted changes to the geometry inside the tips can occur, which affect the properties of the glass fibers.
  • the production is very complex. Especially when the tips are to be precisely positioned.
  • the inner shape of the tips is usually very limited due to the material used and the desired material properties. In the case of a one-piece production, a thick base plate can be rolled, the tips (pressed bases) can be shaped and the rear side can then be milled off to a desired thickness.
  • the disadvantage here is a high use of material and the associated high costs.
  • the object of the invention is to overcome the disadvantages of the prior art.
  • a possibility is to be found of producing and providing a glass fiber nozzle which is as inexpensive as possible and at the same time also allows the implementation of different geometries for the tubes.
  • the glass fiber nozzle must be stable in relation to the glass melt but also in relation to the high temperatures during use. It should be possible to cool the tubes in a controlled manner so that the glass fiber nozzle can be used for as long as possible before it has to be completely replaced or at least repaired.
  • the glass fiber nozzle should be able to produce new glass fibers suitable for special applications.
  • the objects of the invention are achieved by a method for the production of glass fiber nozzles which are provided for the production of glass fibers from a glass melt, the method comprising the steps:
  • the tubes are often referred to as tips on fiberglass nozzles.
  • the at least one tube can therefore at least be a tip.
  • a tube is to be understood as a tube with a general geometry.
  • the tubes are in no way restricted to cylindrical or rotationally symmetrical geometries.
  • the tube can, for example, also have the shape of a torus (donut shape) with an elliptical cross section.
  • the at least one passage in the at least one tube can have a geometry which influences the flow of the glass melt in and through the at least one passage. For example, a rotation of the flowing glass melt can be achieved through the internal shape of the at least one passage.
  • the geometry of the tubes and thus the emerging fibers do not have to be constant over the base plate surface.
  • the shape of the tubes can vary both in terms of size and in terms of shape and geometry.
  • the at least one tube can have a narrowing or widening in the at least one passage.
  • the constriction can then act as a nozzle for ejecting the glass melt to position the glass fiber.
  • the broadening can influence the flow behavior, in particular the flow velocity of the glass melt.
  • the second material is a different material from the first material.
  • a powdery second material or a wire-like second material is preferably used in step B), particularly preferably a powdery second material.
  • the pulverulent second material can preferably have an average grain size of less than 50 ⁇ m. It can be provided that the powdery second material is sieved to limit the particle size, preferably with a sieve of the fraction 200 ⁇ m or smaller, particularly preferably with a sieve of the fraction 100 gm to 50 gm, very particularly preferably with a sieve of the fraction 50 gm.
  • the wire-shaped second material preferably has a diameter of less than 200 gm, preferably less than 50 gm. It can preferably be provided that step C) takes place before step B) or after step B).
  • the base plate can be a sheet, preferably a metallic sheet, particularly preferably a sheet made of a noble metal or a noble metal-based alloy, very particularly preferably a sheet made of platinum or a platinum-based alloy or a platinum-rhodium alloy, especially preferably a sheet made of a PtRh10 alloy.
  • the first material is preferably an oxide-dispersion-hardened platinum (DPH) or an oxide-dispersion-hardened platinum-rhodium alloy, very particularly preferably oxidation-hardened PtRh10.
  • DPH oxide-dispersion-hardened platinum
  • PtRh10 oxide-dispersion-hardened platinum-rhodium alloy
  • the base plate is not made with a laser melting method, a laser sintering method, a
  • Electron beam melting process or an electron beam sintering process is produced.
  • the base plate is not produced using a layered 3D printing method.
  • the base plate can be made particularly stable with respect to the temperature and the chemical environment.
  • step A1) takes place before step A): A1) production of the base plate with a method comprising melt casting and / or rolling, in particular melt casting and subsequent rolling.
  • a particularly stable and high-temperature-resistant base plate can be produced, and at the same time the variability of the printing process can be used for the at least one small tube.
  • a dispersion-strengthened, in particular oxide-dispersion-hardened, metallic material is used as the first material, wherein the first material delimits all surfaces coming into contact with the molten glass.
  • the dispersion-strengthened metallic material used is a dispersion-strengthened noble metal or a dispersion-strengthened noble metal alloy which is dispersion-strengthened with ceramic particles, in particular with ceramic ZrO 2 particles.
  • a platinum or oxide-dispersion-hardened platinum-rhodium alloy is used as the first material with ceramic particles, with oxide particles or with ceramic ZrO2 particles.
  • a dispersion-strengthened PtRhlO alloy is preferably used.
  • the ceramic particles are preferably distributed in the metallic matrix of the first material in order to bring about the solidification of the dispersion.
  • an oxide dispersion strengthened alloy is used as the dispersion strengthened metallic first material.
  • the base plate consists of the first material.
  • the base plate can be manufactured particularly inexpensively.
  • the first material and / or the second material is a metal or a metal alloy, preferably platinum or a platinum-based alloy or a platinum-rhodium alloy, particularly preferably a PtRh10 alloy.
  • a platinum-based alloy is to be understood as an alloy with platinum as the main component. This is preferably understood to mean an alloy with at least 50 atomic percent platinum.
  • step B1) takes place between step A) and step B):
  • step B1) Printing a continuous and / or full-surface coating made of the second material on the side of the base plate, the at least one tube being printed on the continuous and / or full-surface coating of the base plate in step B).
  • Coating can be done using either powder or wire.
  • the base plate can be roughened by the coating, the base plate being roughened at least at the points where the powder for the at least one small tube is intended to adhere.
  • the coating can have a positive effect on the warpage of the base plate when the at least one tube is printed on.
  • a step D) takes place after step B) and after step C): D) Coating the outside of the at least one tube and the side of the base plate on which the at least one tube is printed with a protective layer, in particular with a ceramic protective layer.
  • step B1) takes place before step D), namely printing a continuous or full-surface coating of the second material onto one side of the base plate, with the at least one tube in step B) the continuous or full-surface coating of the base plate is printed on.
  • step B) a tube made of the second material is printed onto one side of the base plate, the tube having at least one passage, and in step C) before step B) or after step B. ) a passage is created in the base plate, the passage through the base plate being connected to at least one of the at least one passage of the tube in such a way that the passage through the base plate with at least one of the at least one passage of the tube has a common and for the glass melt forms a continuous line that leads through the base plate and through the tube.
  • step B) a plurality of tubes made of the second material are printed on one side of the base plate, the tubes each having at least one passage, and in step C) before step B) or after step B) generation several passages takes place in the base plate, the passages through the base plate each being connected to at least one of the at least one passage of one of the tubes in such a way that the passages through the base plate with at least one of the at least one passage of a respective one tube are common and for the Molten glass form continuous lines that lead through the base plate and through the tubes.
  • each of the tubes can be used individually to give off heat, so that the individual tubes heat up less or quickly. This can improve the durability of the fiberglass nozzle.
  • the first material has a higher heat resistance and / or a higher creep resistance than the second material. This ensures that the base plate, which is exposed to the molten glass to a greater extent than the at least one tube, is more chemically stable than the molten glass but is also more stable against the evaporation of constituents from the first material. This will ensure greater durability of the Glass fiber nozzle achieved than if the base plate would also have a lower heat resistance, at the same time the at least one tube can be printed on the base plate in a very variable form with a printing process, even if it has a lower heat resistance as a result.
  • the tubes can have a higher, equal or lower rhodium content than the base plate, so that an optimum can always be found depending on the rhodium price, evaporation rate and stability.
  • Creep also retardation
  • a key figure for creep is the creep rate or Norton exponent (English creep rate and Norton coefficient). At almost constant temperature, the creep rate follows Norton 's creep law.
  • the creep strength describes the maximum stress in order not to exceed a specified creep strain (within a defined time interval). Similarly, the creep rupture strength can be defined as the maximum stress to achieve a specified service life (before breakage occurs).
  • the heat resistance is the strength of a material at elevated temperatures. This means that the strength of the first material at the temperature of the glass melt, in particular at 1400 ° C., is higher than that of the second material.
  • the strength of a material describes the ability to withstand mechanical loads before failure occurs and is specified as mechanical stress (force per cross-sectional area).
  • the failure can be an impermissible deformation, in particular a plastic (permanent) deformation or a break.
  • the strength describes the limit value from which a non-elastic, i.e. irreversible deformation of the material occurs with a defined geometry and load.
  • the mechanical properties can be determined, for example, with a universal testing machine of the Zwick Roell Z100 type from Zwick GmbH & Co. KG.
  • the change in length of the samples of the materials can be recorded using a macro-fine extensometer and the load using a 100 kN load cell. For example, the yield strength
  • Yield strength R P o.2, the tensile strength R m and the elongation at break SB at a
  • Test speed of 3 mm / min at room temperature and / or 1400 ° C can be determined.
  • the evaluation can be carried out, for example, with the testXpert® software from Zwick GmbH & Co. KG.
  • the mechanical properties can be determined, for example, with a universal testing machine of the Zwick Roell Z100 type from Zwick GmbH & Co. KG.
  • the change in length of the samples of the materials can be recorded using a macro-fine extensometer and the load using a 100 kN load cell. For example, the yield point (yield point) R P o.2, the tensile strength R m and the elongation at break SB at a
  • Test speed of 3 mm / min at room temperature and / or 1400 ° C can be determined.
  • the evaluation can be carried out, for example, with the testXpert® software from Zwick GmbH & Co. KG.
  • Oxide-dispersion-hardened platinum (Pt DPH) or oxide-dispersion-hardened platinum-rhodium (PtRh DPH) is preferably used as the first and / or the second material, particularly preferably oxide-dispersion-hardened platinum-rhodium with 10% by weight of Rh and 90% by weight of Pt including production-related impurities (PtRh10 DPH) ).
  • the mechanical high-temperature properties of oxide dispersion hardened platinum (Pt DPH), which is preferably used as the first material, at 1400 ° C are: tensile strength R m 15.6 MPa, yield strength R P o, 2 13.6 MPa, elongation at break A 53% , Creep strength for 10,000 hours 2.5 MPa and creep strength at a creep rate of 10 9 s 1 at 2.4 MPa.
  • the mechanical high-temperature properties of oxide dispersion hardened platinum (PtRh10 DPH) at 1400 ° C are characterized by the tensile strength R m 52 MPa, the yield strength R P o, 240 MPa, the elongation at break A 32%, the creep strength for 10,000 hours 6.8 MPa and the creep strength at a creep rate of 10 -9 s _1 at 8.8 MPa.
  • the first material has a different chemical composition than the second material.
  • the at least one tube is subjected to selective laser melting (SLM), selective laser sintering (SLS), selective electron beam melting (SEBM), laser deposition welding (LMD - “Laser Metal Deposition”), 3D laser plating (DED - “Direct Energy Deposition”) or a selective electron beam sintering (SEBS) is printed on the base plate.
  • SLM selective laser melting
  • SLS selective laser sintering
  • SEBM selective electron beam melting
  • SEBM laser deposition welding
  • DED - “Direct Energy Deposition” 3D laser plating
  • SEBS selective electron beam sintering
  • the at least one tube when the at least one tube is printed on in step B), the following geometric specifications are met: the at least one tube has a change in wall thickness in the axial direction.
  • the wall of the at least one passage has a higher roughness than the surface of the base plate.
  • the at least one tube is printed on in step B), the following geometric specifications are met: the at least one tube is double-walled or multi-walled. Furthermore, it can be provided that the following geometric specifications are met when the at least one tube is printed on in step B): the at least one passage has a narrowing or a widening.
  • the at least one tube is printed in step B): the at least one tube next to the at least one feedthrough channels for fusing or cooling the tube with a fusing medium or cooling medium, the fusing medium or cooling medium can be liquid or gaseous.
  • At least the side of the base plate on which the at least one tube is printed in step B) is cleaned, rolled, sanded, leveled and / or straightened, in particular fine-tuned, before step B) and / or fine-rolled and cleaned. This ensures that the at least one tube, in particular all several tubes, subsequently with a single printing process on the so treated surface of the base plate can be printed or can.
  • the base plate is manufactured with a flat underside, the at least one tube being printed onto the underside in step B).
  • step B) at least three tubes are printed on the base plate and the sequence of the tubes printed one after the other is selected during printing in such a way that mechanical tensioning of the base plate due to local thermal stress during printing is kept low, in particular as a result it is kept to a minimum that no directly adjacent tubes are printed one after the other.
  • the distortion can be compensated by an additional coating or an additional material application by introducing further tensile / compressive stresses.
  • the resulting distortion is recorded optically or capacitively, for example, and an optimal position and quantity (material as well as energy input) for the compensating material application is determined by simulation.
  • tubes can be built up in parallel.
  • the exposure sequence and the build-up sequence are preferably coordinated taking into account the thermally induced warpage.
  • a tube can partially be built up in one layer in order to reduce the thermal gradient.
  • tubes can be built up in parallel on two opposing metal sheets as base plates in order to reduce warpage.
  • step B) the shape of the at least one passage in the at least one tube is selected to be different from a cylindrical geometry or contains a refraction of an otherwise cylindrical geometry, the shape preferably being chosen such that mixing or a twist is brought about on a glass melt flowing through the at least one passage and / or the at least one tube is a plurality of tubes and the leadthroughs of different tubes have different shapes, in particular depending on the position of the tube on the base plate.
  • the method can be used to generate certain desired flow properties of the glass melt flowing through.
  • influences of the position of the tubes for example with regard to their proximity to the walls of a trough of the glass fiber nozzle, can be compensated for by individually adapting the shape of the feedthroughs in order to produce glass fibers that are as uniform as possible.
  • the at least one tube is printed with a widening as a connection to the base plate on the base plate, the enlargement preferably causing an enlargement of the connecting surface between the at least one tube and the base plate.
  • a glass fiber nozzle for producing glass fibers from a glass melt
  • the glass fiber nozzle having a base plate which has a first material or consists of the first material, the first material being chemically resistant to a glass melt and being dispersion strengthened , at least one tube that is printed from a second material, the at least one tube being printed on one side of the base plate, the at least one tube each having at least one feedthrough and the second material being chemically resistant to the glass melt, wherein in the base plate at least one passage is arranged, wherein the at least one passage through the base plate is connected to at least one of the at least one passage of one of the at least one tube in such a way that each of the at least one passage through the base plate with little At least one of the at least one passage of an associated tube of the at least one tube forms a common line that is continuous for the molten glass and leads through the base plate and through the associated tube, the base plate being produced using a different method than the at least one tube.
  • the printed second material does not have to be inserted or imprinted into holes in the base plate. This keeps the amount of the printed second material low, thereby improving the durability of the glass fiber nozzle and at the same time keeping the costs for its production low.
  • the glass fiber nozzle is produced using a method according to the invention.
  • the glass fiber nozzle has the advantages mentioned for the method for its production.
  • the objects on which the present invention is based are also achieved by a method for producing glass fibers from a glass melt with a glass fiber nozzle according to the invention, in which the glass melt passes through the at least one passage in a base plate and through the at least one passage in the at least one onto the base plate printed tube flows and solidifies after flowing out of the at least one tube to at least one glass fiber. Provision can be made for the method to produce a homogenization of the glass melt in the at least one passage, the internal shape of the at least one passage preferably causing the glass melt to be thoroughly mixed.
  • the invention is based on the surprising finding that by printing the at least one tube onto the base plate, it is possible to enable a high degree of variability in the tube geometry, while at the same time using a base plate produced using a different method there is the possibility of placing the base plate on others to optimize physical parameters, for example with regard to the chemical durability of the base plate in relation to the glass melt or with regard to the high temperature resistance of the base plate.
  • only a small amount of the printing medium needs to be consumed compared to if the entire continuous line (s) or even the entire base plate were printed together with the at least one tube would be printed.
  • welding of the at least one tube to the base plate can be avoided and weak points of the glass fiber nozzle at the weld seams can be avoided. Due to the greater roughness of the inner surfaces of the at least one passage of the at least one tube, better mixing of the glass melt when flowing through can be achieved than if the at least one passage had smooth walls.
  • the strength of the floor slab can be maintained by means of a larger load-bearing cross-section by printing directly onto a stable, conventionally manufactured floor slab, with only a minimal welding zone, which has a reduced strength, and with a smaller pre-drilling diameter required in the floor slab.
  • the method according to the invention and the glass fiber nozzle according to the invention also result in advantages compared to completely 3D-printed bushing bases including small tubes (tips).
  • a different method for producing the base plate can be used than 3D printing for the tubes and thus a more stable result can be achieved and / or a more cost-effective production method can be used will.
  • a high-strength, oxide-dispersion-strengthened platinum or a high-strength, oxide-dispersion-strengthened platinum-rhodium alloy can be used for the base plate, which means that the long-term stability of such a bushing is significantly higher than that of fully printed bushing bases. This is because these cannot be printed as oxide dispersion-strengthened platinum variants or platinum-rhodium variants. Shrinkage of the base plate can also be avoided if it is cast and / or rolled, for example.
  • New tube geometries that cannot be produced using conventional methods can be realized. Because the at least one tube is 3D-printed and not produced by machine subtractively (turned, milled), more complex geometries are possible, which have a positive effect on the glass fiber quality and output and which would not be possible with subtractive processes.
  • the present invention therefore proposes a direct 3D printing of the glass fiber tips (the at least one small tube) on a base plate made of a noble metal alloy or of another suitable combination of materials.
  • the base plate can already be perforated, or the holes (of the at least one passage) can be produced after the tips (of the at least one tube) have been printed on.
  • the shape of the tips can be implemented in a geometry desired by the user. Here are different cross-sections, wall thickness profiles, flow-influencing geometries and
  • the tips or tubes can be built onto the base plate (for example a sheet of metal) using any 3D printing process. A measurement may be necessary to enable rework.
  • the base plate can be cleaned, leveled, polished and / or coated, for example.
  • a structured 3D-printed surface inside or outside the at least one tube can be advantageous in order to optimize the component properties in terms of flow mechanics (inside) or to provide the component with an adhesive coating that reduces or completely reduces the evaporation of platinum and / or rhodium prevented.
  • the glass fibers produced with a method according to the invention are technical glass fibers which are suitable for applications such as, for example, glass fiber reinforced plastics, the electronics industry (glass fiber reinforced circuit boards) and the textile industry (refractory fabrics).
  • exemplary embodiments of the invention are explained on the basis of eleven figures, without, however, restricting the invention. It shows:
  • FIG. 1 a schematic perspective view of the underside of a base plate of a glass fiber nozzle according to the invention
  • FIG. 2 a schematic perspective view (FIG. 2 above) and a schematic perspective cross-sectional view (FIG. 2 below) of a printed tube (tip) of a glass fiber nozzle according to the invention;
  • FIG. 3 a schematic perspective cross-sectional view of a third exemplary tube (tip) for a glass fiber nozzle according to the invention
  • FIG. 4 a schematic perspective cross-sectional view of a fourth exemplary tube (tip) for a glass fiber nozzle according to the invention
  • FIG. 5 a schematic perspective cross-sectional view of a fifth exemplary tube (tip) for a glass fiber nozzle according to the invention
  • FIG. 6 a schematic perspective cross-sectional view of a sixth exemplary tube (tip) for a glass fiber nozzle according to the invention
  • FIG. 7 a schematic perspective cross-sectional view of a seventh exemplary tube (tip) for a glass fiber nozzle according to the invention
  • FIG. 8 a schematic perspective cross-sectional view of an eighth exemplary tube (tip) for a glass fiber nozzle according to the invention.
  • FIG. 9 a schematic cross-sectional view of a glass fiber nozzle according to the invention.
  • FIG. 10 a schematic cross-sectional view of a production of a glass fiber nozzle according to the invention.
  • FIG. 11 the sequence of a method according to the invention as a flow chart.
  • FIG. 1 shows a schematic perspective view of the underside of a base plate 1 of a glass fiber nozzle according to the invention.
  • a base plate 1 On the underside of the base plate 1, several tubes 2, which are also referred to as tips, can be inserted into two rows can be arranged offset to one another.
  • the tubes 2 can be printed onto the underside of the base plate 1 using a 3D printing process.
  • a metal powder (not shown) can be melted, welded or sintered in layers with the aid of a laser in order to build up the tubes 2 in layers on the base plate 1.
  • a metal wire can also be used together with a laser material deposition process (LMD process).
  • LMD process laser material deposition process
  • the base plate 1 can have a step 3 via which the base plate 1 can be connected to side walls (not shown) (analogous to FIG. 9) in order to form a container for a glass melt (not shown) for a glass fiber nozzle.
  • Each tube 2 can have a continuous passage 4 which extends to the base plate 1.
  • Passages are arranged in the base plate 1 (cannot be seen in FIG. 1).
  • the passages can open into the feedthroughs 4 within the tubes 2.
  • the passages can connect the underside of the base plate 1 to the top side of the base plate 1.
  • the passages can be aligned with the feedthroughs 4 and thus form a common line which is permeable to a glass melt.
  • the glass melt can then flow out of the feed-throughs 4 through the base plate 1 and through the tubes 2. During the subsequent solidification of the glass melt, glass fibers are formed.
  • the base plate 1 itself can consist of an oxide-dispersion-hardened metal or an oxide-dispersion-hardened metal alloy, in particular an oxide-dispersion-hardened platinum or an oxide-dispersion-hardened platinum-rhodium alloy, particularly preferably PtRh10 DPH.
  • ceramic or other oxidic particles can be distributed in the metal or the metal alloy.
  • FIG. 2 shows a second exemplary embodiment of a tube 12 which can be printed onto a base plate (not shown in FIG. 2) in order to realize a glass fiber nozzle according to the invention.
  • the tube 12 is shown completely in a schematic perspective view at the top in FIG. 2 and in a schematic perspective cross-sectional view at the bottom in FIG. 2.
  • a continuous cylindrical passage 14 can be arranged in the tube 12.
  • the side of the tube 12 fastened to the base plate (not shown) can have a widening 15 in the form of a Exhibit foot. The widening 15 enlarges the connection area to the base plate and can thus bring about a more stable connection between the base plate and the tube 12.
  • the tube 12 can have a conical tip 16 on its side opposite the widening 15.
  • the conical tip 16 has the effect that the molten glass can flow out of the feedthrough 14 more evenly.
  • the tube 12 can be printed in layers from a metal powder on a base plate (not shown).
  • a metal wire can also be used together with a laser material deposition process (LMD process).
  • LMD process laser material deposition process
  • several of these tubes 12 are printed on the base plate.
  • a passage can be provided in the base plate for each tube 12 (see FIG. 9).
  • the tube 12 can be positioned or printed on the base plate in such a way that the passage is aligned with the feedthrough 14 and thus both form a common line for the glass melt.
  • FIGS. 3 to 8 Due to the use of a 3D printing process, a wide variety of different shapes and geometries can be used to manufacture tubes.
  • FIGS. 3 to 8 six further exemplary embodiments for small tubes 22, 32, 42, 52, 62, 72 are shown, which are suitable for realizing a glass fiber nozzle according to the invention individually, in large numbers or mixed with one another.
  • FIG. 3 shows a third exemplary embodiment of a tube 22 which can be printed onto a base plate, which is not shown in FIG. 3, in order to realize a glass fiber nozzle according to the invention.
  • the tube 22 is shown in Figure 3 in a schematic perspective cross-sectional view.
  • a through passage 24 can be arranged in the tube 22.
  • the side of the tube 22 fastened to the base plate (not shown) can have a widening 25 in the form of a foot. The widening 25 enlarges the connection area to the base plate and can thus bring about a more stable connection between the base plate and the tube 22.
  • the tube 22 can have a conical tip 26 on its side opposite the widening 25.
  • the conical tip 26 causes the glass to melt can flow out of the implementation 24 more evenly.
  • the passage 24 can be shaped rotationally symmetrically and shaped cylindrically in the area of the widening 25 and the conical tip 26.
  • a circumferential bead-like thickening 27 of the wall of the passage 24 can be arranged in the passage 24.
  • the thickening 27 of the wall leads to a constriction 28 of the passage 24 in the area of the thickening 27.
  • the constriction 28 causes a change in the flow of a glass melt which flows through the passage 24.
  • the constriction 28 can, for example, change the flow velocity as a function of the radius perpendicular to the flow in the glass melt.
  • the glass melt can be mixed directly before it flows out of the conical tip 26 of the tube 22.
  • the tube 22 can be printed in layers on a base plate (not shown) made of a metal powder, in particular a platinum powder or a platinum-rhodium powder, particularly preferably a powder made of PtRhl 0 DPH.
  • a metal wire can also be used together with a laser material deposition process (LMD process).
  • LMD process laser material deposition process
  • several of these tubes 22 are printed on the base plate.
  • a passage can be arranged in the base plate for each tube 22 (see FIG. 9).
  • the tube 22 can be positioned or printed on the base plate in such a way that the passage is aligned with the feed-through 24 and thus both form a common line for the glass melt.
  • FIG. 4 shows a fourth exemplary embodiment of a tube 32 which can be printed onto a base plate, which is not shown in FIG. 4, in order to realize a glass fiber nozzle according to the invention.
  • the tube 32 is shown in FIG. 4 in a schematic perspective cross-sectional view.
  • the tube 32 is shown in FIG. 4 in a schematic perspective cross-sectional view.
  • a through passage 34 can be arranged in the tube 32.
  • the side of the tube 32 fastened to the base plate (not shown) can have a widening 35 in the form of a foot. The widening 35 enlarges the connection area to the base plate and can thus bring about a more stable connection between the base plate and the tube 32.
  • the tube 32 can have a conical tip 36 on its side opposite the widening 35.
  • the conical tip 36 causes the glass to melt can flow more evenly from the implementation 34.
  • the passage 34 can be shaped essentially rotationally symmetrically and can be shaped cylindrically in the area of the widening 35 and the conical tip 36.
  • a circumferential, spherical segment-shaped thinning 37 of the wall of the passage 34 can be arranged.
  • the thinning 37 of the wall leads to a widening 38 of the passage 34 in the area of the thinning 37.
  • coiled projecting strips 39 can be arranged on the inside of the wall, which act as a thread to a torque flowing through the passage 34 Causing molten glass
  • the widening 38 and the strips 39 cause a change in the flow of a molten glass which flows through the passage 34.
  • the widening 38 can, for example, change the flow velocity as a function of the radius perpendicular to the flow in the glass melt.
  • the glass melt can be mixed directly before it flows out of the conical tip 36 of the tube 32.
  • the tube 32 can be printed in layers from a metal powder, in particular from a platinum powder or a platinum-rhodium powder, particularly preferably from a powder of PtRhlO DPH, on a base plate (not shown).
  • a metal wire can also be used together with a laser material deposition process (LMD process).
  • LMD process laser material deposition process
  • a plurality of these tubes 32 are preferably printed onto the base plate.
  • a passage can be arranged in the base plate for each tube 32 (see FIG. 9).
  • the tube 32 can be positioned or printed on the base plate in such a way that the passage is aligned with the feed-through 34 and thus both form a common line for the glass melt.
  • FIG. 5 shows a fifth exemplary embodiment of a tube 42 which can be printed onto a base plate, which is not shown in FIG. 5, in order to realize a glass fiber nozzle according to the invention.
  • the tube 42 is shown in FIG. 5 in a schematic perspective cross-sectional view.
  • a through passage 44 can be arranged in the tube 42.
  • the side of the tube 42 fastened to the base plate (not shown) can have a widening 45 in the form of a foot. The widening 45 increases the connection area to the base plate and can thus bring about a more stable connection between the base plate and the tube 42.
  • the tube 42 can have a conical tip 46 on its side opposite the widening 45.
  • the conical tip 46 has the effect that the molten glass can flow out of the feed-through 44 more evenly.
  • the passage 44 can be shaped rotationally symmetrical and can be shaped cylindrically in the area of the widening 45 and the conical tip 46.
  • a circumferential, spherical segment-shaped thinning 47 of the wall of the passage 44 can be arranged in the passage 44.
  • the thinning 47 of the wall leads to a widening 48 of the passage 44 in the area of the thinning 37.
  • the widening 48 causes a change in the flow of a glass melt flowing through the passage 44.
  • the widening 48 can, for example, change the flow velocity as a function of the radius perpendicular to the flow in the glass melt.
  • the glass melt can be mixed directly before it flows out of the conical tip 46 of the tube 42.
  • the tube 42 can be printed in layers from a metal powder, in particular from a platinum powder or a platinum-rhodium powder, particularly preferably from a powder of PtRhlO DPH, on a base plate (not shown).
  • a metal wire can also be used together with a laser material deposition process (LMD process).
  • LMD process laser material deposition process
  • a plurality of these tubes 42 are preferably printed onto the base plate.
  • a passage can be arranged in the base plate for each tube 42 (see FIG. 9).
  • the tube 42 can be positioned or printed on the base plate in such a way that the passage is aligned with the feedthrough 44 and thus both form a common line for the glass melt.
  • FIG. 6 shows a sixth exemplary embodiment of a tube 52 which can be printed onto a base plate, which is not shown in FIG. 6, in order to realize a glass fiber nozzle according to the invention.
  • the tube 52 is shown in FIG. 6 in a schematic perspective cross-sectional view.
  • a through passage 54 can be arranged in the tube 52.
  • the side of the tube 52 fastened to the base plate (not shown) can have a widening 55 in the form of a foot. The widening 55 increases the connection area to the base plate and can thus bring about a more stable connection between the base plate and the tube 52.
  • the tube 52 can have a conical tip 56 on its side opposite the widening 55.
  • the conical tip 56 has the effect that the molten glass can flow out of the feedthrough 54 more evenly.
  • the feedthrough 54 can be largely cylindrical and can be completely cylindrical in the area of the widening 55 and the conical tip 56.
  • a core 57 can be arranged in the middle, that is to say on the cylinder axis of the cylindrical passage 54.
  • the core 57 can be held with five webs 58, the webs 58 connecting the core 57 to the inner wall of the passage 54.
  • the webs 58 can protrude from the inner wall of the passage 54 at an angle against the intended flow direction of the glass melt.
  • the core 57 and to a certain extent also the webs 58 cause a change in the flow of a glass melt flowing through the passage 54.
  • the core 57 can, for example, slow down the flow rate of the flow in the glass melt in the middle of the passage 54.
  • the glass melt can be mixed directly before it flows out of the conical tip 56 of the tube 52.
  • the tube 52 can be printed in layers from a metal powder, in particular from a platinum powder or a platinum-rhodium powder, particularly preferably from a powder of PtRh10 DPH, on a base plate (not shown).
  • a metal wire can also be used together with a laser material deposition process (LMD process).
  • LMD process laser material deposition process
  • a plurality of these tubes 52 are preferably printed on the base plate.
  • a passage can be arranged in the base plate for each tube 52 (see FIG. 9).
  • the tube 52 can be positioned or printed on the base plate in such a way that the passage is aligned with the feed-through 54 and thus both form a common line for the glass melt.
  • FIG. 7 shows a seventh exemplary embodiment of a tube 62 which can be printed onto a base plate, which is not shown in FIG. 7, in order to realize a glass fiber nozzle according to the invention.
  • the tube 62 is shown in Figure 7 in a schematic perspective cross-sectional view.
  • a continuous central Implementation 64 can be arranged in the tube 62.
  • the side of the tube 62 fastened to the base plate (not shown) can have a widening 65 in the form of a foot. The widening 65 increases the connection area to the base plate and can thus produce a more stable connection between the base plate and the tube 62.
  • the tube 62 can have a conical tip 66 on its side opposite the widening 65.
  • the conical tip 66 has the effect that the glass melt can flow more evenly out of the central passage 64.
  • the central passage 64 can be cylindrical in shape.
  • several outer, continuous leadthroughs 67 can be arranged, which open into the central leadthrough 64 via junctions 68 in the area of the conical tip 66.
  • the outer passages 67 can be tubular and preferably cylindrical in certain areas.
  • the central passage 64 can have a larger diameter than the outer passages 67.
  • the glass melt can flow through the central passage 64 and through the outer passages 67 during operation of the glass fiber nozzle.
  • the glass melt can be mixed directly before it flows out of the conical tip 66 of the tube 62.
  • the tube 62 can be printed in layers from a metal powder, in particular from a platinum powder or a platinum-rhodium powder, particularly preferably from a powder of PtRhl 0 DPH, on a base plate (not shown).
  • a metal wire can also be used together with a laser material deposition process (LMD process).
  • LMD process laser material deposition process
  • a plurality of these tubes 62 are preferably printed onto the base plate.
  • a passage can be arranged in the base plate for each tube 62 (see FIG. 9).
  • FIG. 8 shows an eighth exemplary embodiment of a tube 72 which can be printed onto a base plate, which is not shown in FIG. 8, in order to realize a glass fiber nozzle according to the invention.
  • the tube 72 is shown in FIG. 8 in a schematic perspective cross-sectional view.
  • a through passage 74 can be arranged in the tube 72.
  • the side of the tube 72 fastened to the base plate can have a widening 75 in the form of a foot.
  • the widening 75 enlarges the connection area to the base plate and can thus bring about a more stable connection between the base plate and the tube 72.
  • the tube 72 can have a conical tip 76 on its side opposite the widening 75.
  • the conical tip 76 has the effect that the glass melt can flow out of the passage 74 more evenly.
  • the passage 74 can be shaped in the manner of a thread with a very steep pitch and otherwise be shaped cylindrically.
  • a plurality of circumferential, wound grooves 77 of the wall of the passage 74 can be arranged in the passage 74.
  • the winding grooves 77 can transmit a torque to a glass melt flowing through the passage 74 and thus cause a change in the flow of a glass melt flowing through the passage 74.
  • the glass melt can be mixed directly before it flows out of the conical tip 76 of the tube 72.
  • the tube 72 can be printed in layers from a metal powder, in particular from a platinum powder or a platinum-rhodium powder, particularly preferably from a powder of PtRhl 0 DPH, on a base plate (not shown).
  • a metal wire can also be used together with a laser material deposition process (LMD process).
  • LMD process laser material deposition process
  • a plurality of these tubes 72 are preferably printed onto the base plate.
  • a passage can be arranged in the base plate for each tube 72 (see FIG. 9).
  • the tube 72 can be positioned or printed on the base plate in such a way that the passage is aligned with the feed-through 74 and thus both form a common line for the glass melt.
  • FIG. 9 shows a schematic cross-sectional view of a glass fiber nozzle according to the invention.
  • the fiberglass nozzle can have a base plate 81 with several Have passages 80.
  • a plurality of tubes 82, 92, which are also referred to as tips, can be arranged on the underside of the base plate 81.
  • the tubes 82, 92 can be printed onto the underside of the base plate 81 using a 3D printing process.
  • a metal powder (not shown) can be melted, welded or sintered in layers with the aid of a laser in order to build up the tubes 82, 92 in layers on the base plate 81.
  • the tubes 82, 92 can be printed around the passages 80 or, after the tubes 82, 92 have been printed, the passages 80 can be drilled into the base plate 81 or produced in some other way in the base plate 81.
  • the base plate 81 can have a step 83 via which the base plate 81 can be connected to circumferential side walls 89 in order to form a container for a glass melt (not shown) for the glass fiber nozzle.
  • Each tube 82, 92 can have a through passage 84, 94 that extends as far as the base plate 81.
  • the passages 80 can open into the passages 84, 94 within the tubes 82, 92.
  • the passages 80 can connect the lower side of the base plate 81 to the upper side of the base plate 81.
  • the feedthroughs 84, 94 can be aligned with the passages 80, so that the feedthroughs 84, 94 with the passages 80 form a common line for the glass melt.
  • the glass melt can then flow out of the feed-throughs 84, 94 through the base plate 81 and through the tubes 82, 92. During the subsequent solidification of the glass melt, glass fibers are formed.
  • the base plate 81 itself can consist of an oxide-dispersion-hardened metal or an oxide-dispersion-hardened metal alloy, in particular of an oxide-dispersion-hardened platinum or an oxide-dispersion-hardened platinum-rhodium alloy, particularly preferably of PtRh10 DPH.
  • ceramic or other oxidic particles can be distributed in the metal or the metal alloy.
  • the tubes 82, 92 according to FIG. 8 represent ninth and tenth exemplary designs which are printed on the base plate 81.
  • the sides of the tubes 82, 92 fastened to the base plate 81 can have widenings 85, 95 in the form of
  • the widenings 85, 95 enlarge the connection area to the base plate 81 and can thus bring about a more stable connection between the base plate 81 and the tubes 82, 92. It can also be provided that the entire side of the base plate 81 on which the tubes 82, 92 are printed (bottom in FIG. 8), is printed with a thin layer (not visible in FIG. 8) made of the same material as the tubes 82, 92.
  • the tubes 82, 92 can have conical tips 86, 96 on their sides opposite the widening 85, 95.
  • the conical tips 86, 96 have the effect that the glass melt can flow out of the feedthroughs 84, 94 more evenly.
  • the passages 84, 94 can be shaped rotationally symmetrically and shaped cylindrically in the area of the widened areas 85, 95 and the conical tips 86, 96. Circumferential bead-like thickenings 87, 97 of the walls of the passages 84, 94 can be arranged in the passages 84, 94.
  • the thickenings 87, 97 of the wall lead to the formation of constrictions 88, 98 in the passages 84, 94 in the area of the thickenings 87, 97.
  • the constrictions 88, 98 cause a change in the flow of a glass melt flowing through the passages 84, 94 .
  • the constrictions 88, 98 can, for example, change the flow velocity as a function of the radius perpendicular to the flow in the glass melt.
  • the glass melt can be mixed directly before it flows out of the conical tips 86, 96 of the tube 82, 92.
  • the middle tube 92 has a narrower constriction 98 of the feedthrough 94 than the constrictions 88 of the feedthroughs 84 of the two outer tubes 82.
  • the tubes 82, 92 can be printed in layers on the base plate 81 from a metal powder, in particular from a platinum powder or a platinum-rhodium powder, particularly preferably from a powder made of PtRh10 DPH.
  • a metal wire can also be used together with a laser material deposition process (LMD process).
  • LMD process laser material deposition process
  • the layers for building up these tubes 82, 92 are preferably printed on the base plate 81 in such a way that two tubes 82, 92 that are spatially adjacent to one another are not printed directly one after the other on the base plate 81. As a result, the heat generated during the printing process can flow away better and local overheating of the base plate 81 is less likely.
  • a passage 80 can be provided in the base plate 81 for each tube 82, 92.
  • the tubes 82, 92 can be positioned or printed on the base plate 81 in such a way that each of the passages 80 is aligned with exactly one of the passages 84, 94 and thus both form a common line for the glass melt.
  • the sequence of a method according to the invention is described below with reference to FIGS. 10 and 9.
  • the base plate 81 can be produced from the melt by casting. In the process, oxidic particles can be distributed or generated in the melt. After the melt has solidified, in a second work step 101 the base plate 81 can be shaped and further hardened by rolling and / or by a further temperature treatment. The step 83 can also be introduced into the base plate 81.
  • the underside of the base plate 81 can be leveled and / or pretreated and cleaned so that it can then be printed on.
  • the base plate 81 can be made available for printing.
  • the base plate 81 can be fastened in a 3D printer.
  • a base plate 81 produced using a method other than the method specified in the following fifth work step 104 can also be provided. The method according to the invention can therefore begin with the fourth work step 103.
  • the tubes 82, 92 can be printed in layers on the base plate 81.
  • a powder (not shown) can be melted, sintered or welded in layers with a laser onto the base plate 81 or onto previous layers.
  • the surface of the base plate 81 with the tubes 82, 92 can be cleaned, recompacted, polished or coated.
  • a ceramic coating can be applied to the surface of the underside of the base plate (if printed), which is rough due to the 3D printing, and to the outside of the tubes 82, 92.
  • the base plate 81 can be welded to circumferential side walls 89 or connected in some other way will. The side walls 89 can be produced beforehand using the same method as the base plate 81.
  • a glass fiber nozzle according to the invention is obtained.
  • the side walls 89 and the base plate 81 can form a container for a glass melt.
  • the glass melt can flow out of this container through the passages 80 and the passages 84, 94 and the glass fibers are thus formed.
  • the same process can also be used to produce glass fiber nozzles with tubes with other geometries, such as the geometries shown in FIGS. 2 to 7, for example.
  • the geometries can easily be mixed as desired.
  • FIG. 11 shows a schematic cross-sectional view of a freeing position of a glass fiber nozzle according to the invention.
  • Several tubes 112 can be built up on two base plates 111 using a laser process.
  • the base plates 111 can be sheets made of dispersion-hardened platinum or dispersion-hardened PtRh10 alloy.
  • Semi-finished tubes 113 under construction on the base plates 111 are also shown in FIG.
  • the base plates 111 can be fastened on both sides on a carrier 114 and two lasers 116 can be used for the bilateral and parallel construction.
  • the laser beams 118 can hit the semi-finished tubes 113 for additive manufacturing, as is shown in FIG. 11.
  • the carrier 114 may be mounted on a stand 120.
  • LMD Laser metal deposition
  • DED 3D laser plating
  • tubes 112 can be built up in parallel on two oppositely attached base plates 111 in order to reduce warpage.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Manufacture, Treatment Of Glass Fibers (AREA)

Abstract

L'invention se rapporte à un procédé de production de buses pour fibre de verre comprenant les étapes suivantes consistant : A) à fournir ou produire une plaque de base (81) comprenant un premier matériau, le premier matériau étant chimiquement résistant à la masse de verre fondue et étant durci par dispersion ; B) à presser au moins un tube (82, 92), constitué d'un deuxième matériau, sur une face de la plaque de base (81), le ou les tubes (82, 92) comprenant, dans chaque cas, au moins une traversée (84, 94) et le second matériau étant chimiquement résistant à la masse de verre fondue ; C) à produire au moins un passage (80) dans la plaque de base (81), le ou les passages (80) à travers la plaque de base (81) étant reliés à au moins l'une de la ou des traversées (84, 94), dans chaque cas, d'un tube parmi lesdits au moins un tubes (82, 92) de sorte que chacun desdits au moins un passage (80) à travers la plaque de base (81) forme, conjointement avec au moins l'une de la ou des traversées (84, 94) d'un tube associé (82, 92) dudit au moins un tube (82, 92), une ligne commune à travers laquelle peut passer la masse de verre fondue, laquelle ligne passe à travers la plaque de base (81) et à travers le tube associé (82, 92), et la plaque de base (181) étant produite à l'aide d'un procédé différent de celui du ou des tubes (82, 92). L'invention se rapporte également à une buse pour fibre de verre destinée à produire des fibres de verre et à un procédé de production de fibres de verre.
EP21705920.3A 2020-03-12 2021-02-12 Procédé de production de buses pour fibre de verre et buse pour fibre de verre Pending EP4118042A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020106745.3A DE102020106745A1 (de) 2020-03-12 2020-03-12 Verfahren zur Herstellung von Glasfaserdüsen und Glasfaserdüse
PCT/EP2021/053467 WO2021180420A1 (fr) 2020-03-12 2021-02-12 Procédé de production de buses pour fibre de verre et buse pour fibre de verre

Publications (1)

Publication Number Publication Date
EP4118042A1 true EP4118042A1 (fr) 2023-01-18

Family

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Application Number Title Priority Date Filing Date
EP21705920.3A Pending EP4118042A1 (fr) 2020-03-12 2021-02-12 Procédé de production de buses pour fibre de verre et buse pour fibre de verre

Country Status (6)

Country Link
EP (1) EP4118042A1 (fr)
JP (1) JP7393559B2 (fr)
KR (1) KR20220149719A (fr)
CN (1) CN115279706A (fr)
DE (1) DE102020106745A1 (fr)
WO (1) WO2021180420A1 (fr)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1471690A (fr) * 1963-05-06 1967-03-03 Owens Corning Fiberglass Corp Structures stratifiées d'alliages métalliques
DE2852264A1 (de) * 1978-12-02 1980-06-12 Heraeus Gmbh W C Glasfaserspinnduese aus einer edelmetallegierung
US4846865A (en) * 1988-03-15 1989-07-11 Owens-Corning Fiberglas Corporation Clad precious metal bushing and method for making
DE10229952B4 (de) 2002-07-03 2007-08-30 Cl Schutzrechtsverwaltungs Gmbh Metallisches Werkstück sowie Verfahren zur Herstellung desselben
JP2008044801A (ja) * 2006-08-11 2008-02-28 Nippon Electric Glass Co Ltd ガラス繊維製造装置とガラス繊維の製造方法
DE102012008369A1 (de) 2012-04-25 2013-10-31 Airbus Operations Gmbh Verfahren zum Herstellen eines fluidführenden Bauteils durch schichtweisen Aufbau
US20160312338A1 (en) 2015-04-27 2016-10-27 John Hart Miller High hot creep resistant alloys, parts, systems and methods

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JP2023518193A (ja) 2023-04-28
WO2021180420A1 (fr) 2021-09-16
JP7393559B2 (ja) 2023-12-06
DE102020106745A1 (de) 2021-09-16
KR20220149719A (ko) 2022-11-08
CN115279706A (zh) 2022-11-01

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Owner name: HERAEUS PRECIOUS METALS GMBH & CO. KG