EP3077556B1 - Procédé d'usinage d'un matériau à base de platine renforcé par dispersion - Google Patents

Procédé d'usinage d'un matériau à base de platine renforcé par dispersion Download PDF

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Publication number
EP3077556B1
EP3077556B1 EP14812166.8A EP14812166A EP3077556B1 EP 3077556 B1 EP3077556 B1 EP 3077556B1 EP 14812166 A EP14812166 A EP 14812166A EP 3077556 B1 EP3077556 B1 EP 3077556B1
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dispersion
temperature
hardened platinum
hardened
cold forming
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EP3077556A1 (fr
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Dirk Maier
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Heraeus Deutschland GmbH and Co KG
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Heraeus Deutschland GmbH and Co KG
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Classifications

    • 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
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1078—Alloys containing non-metals by internal oxidation of material in solid state
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the invention relates to a method for processing a dispersion-hardened platinum composition. Further, the present invention describes a process for producing a product from a dispersion-hardened platinum composition. Furthermore, the present invention relates to a product obtainable from the methods set out above and the use of such platinum compositions.
  • Platinum shaped bodies are frequently used in high-temperature processes in which the material must have high corrosion resistance.
  • platinum components are used in the glass industry which are mechanically stressed, such as stirrers or glass fiber nozzle trays.
  • a disadvantage of platinum as a material is its low mechanical strength at high temperatures. Therefore, dispersion hardened platinum compositions are generally used for the aforementioned high temperature processes.
  • a billet is generally first produced which is hot-rolled.
  • the resulting semi-finished product can then be cold-formed.
  • the object of the invention is therefore to overcome the disadvantages of the prior art.
  • the method should be a cost-effective adaptation of components of platinum compositions to individual needs while improving the mechanical Enable properties.
  • the components obtained should show a long service life and the lowest possible wear.
  • the method should be simple and inexpensive to carry out.
  • the formed components should have a good processability, in particular weldability.
  • the surface area of that surface is to be understood, which is formed at an (imaginary) section through the solid.
  • the plane spanned by the cross-sectional area may or may not be perpendicular or substantially perpendicular to the longest extent of the solid.
  • weight percentages set out above add up to 100%, the weight of the non-noble metals being based on the weight of metal.
  • the non-noble metal or non-noble metals are at least 70%, preferably at least 90% oxidized with oxygen.
  • all oxidation states of the non-noble metals are taken into account so that preferably at most 30 atomic%, particularly preferably at most 10 atomic% of the non-noble metal is present as metal, that is to say in the formal oxidation state 0.
  • Solid bodies with low levels of non-noble metal oxides show advantages in terms of processability, for example weldability of the solid bodies.
  • a solid is provided.
  • the term solid is to be understood here comprehensively.
  • a solid can be configured for example in the form of a sheet, a pipe or a wire.
  • the sheets, tubes or wires provided may have a thickness in the range of 0.1 mm to 10 mm, preferably 0.3 to 5 mm.
  • the thickness refers to the minimum extent of a solid.
  • a wire this is the diameter and for a pipe, the difference between the outer and inner radius, which is also referred to as the wall thickness of the pipe.
  • the platinum composition which can be used according to the invention comprises at least 70% by weight of platinum and a maximum of 29.95% by weight of other noble metals. Accordingly, the composition may consist essentially of platinum and the at least partially oxidized non-noble metals set forth above.
  • the platinum material may therefore be pure platinum except for customary impurities, in which the at least partially oxidized non-noble metals are mixed in.
  • the platinum composition may also comprise other precious metals, the platinum composition in this case being a platinum alloy.
  • the other precious metals are selected from ruthenium, rhodium, gold, palladium and iridium.
  • the provided solid is cold formed according to the inventive method.
  • the term "cold working" is known in the art, which forming takes place at relatively low temperatures below the recrystallization temperature of the platinum composition, and particularly includes drawing, pressing, deep drawing, cold rolling, cold hammering and pressing.
  • Deformation involves deformation of the bulk body over a large area.
  • the volume body is subjected to deformation over at least 50%, more preferably over at least 75% and especially preferably over at least 95% of the volume.
  • a sheet is preferably at least 50%, more preferably at least 75%, and more preferably at least 95% of the surface area of the sheet subjected to a force or pressure, for example, rolled.
  • the surface can be simplified in relation to the surfaces, which is perpendicular to the minimum extent of the volume body (thickness).
  • the solid is a wire or a tube, preferably at least 50%, more preferably at least 75%, and most preferably at least 95% of the length of the wire or tube is subjected to a force such as pulled.
  • the cross-sectional area of the volume body of the dispersion-hardened platinum composition is reduced by a maximum of 20%, more preferably by a maximum of 18%, and especially preferably by a maximum of 15%.
  • These values are related to the cross-sectional area of the volume, which is maximally reduced.
  • the reduced cross-sectional area results, for example, from the thickness and the unstretched expansion of the solid.
  • the reduction of the cross-sectional area results from the change of the diameter or the wall thickness.
  • the volume of the body is not changed by the deformation, at least one cross-sectional area must be increased during a forming.
  • the length will increase during forming, so that the surface becomes larger in the direction of increasing the length.
  • the directions in which the deforming forces act in particular parallel or perpendicular to the plane, which is spanned by the cross-sectional area.
  • the cross-sectional area of the volume body of the dispersion-hardened platinum composition is reduced by at least 5%, preferably reduced by at least 8%, and particularly preferably reduced by at least 10%.
  • a wire is drawn or pressed, wherein in the cold forming the cross-sectional area of the wire from the dispersion-hardened platinum composition is reduced by a maximum of 20%, more preferably by a maximum of 18% and more preferably by a maximum of 15% or by cold forming a sheet is rolled, drawn, pressed or pressed, wherein in the cold forming, the cross-sectional area of the sheet or the thickness of the sheet of the dispersion-hardened platinum composition is reduced by a maximum of 20%, more preferably by a maximum of 18% and more preferably by a maximum of 15% or Cold forming a tube is rolled, drawn or pressed, wherein in the cold forming, the cross-sectional area of the tube of the dispersion-hardened platinum composition is reduced by a maximum of 20%, more preferably by a maximum of 18% and more preferably by a maximum of 15%.
  • a temperature treatment of the cold-formed volume body is carried out, in which the cold-worked product is annealed at at least 1100 ° C for at least one hour.
  • the annealing may preferably take place over a period of at least 90 minutes, preferably at least 120 minutes, more preferably at least 150 minutes, and especially preferably at least 180 minutes.
  • the temperature at which the annealing is carried out may preferably be at least 1200 ° C, more preferably at least 1250 ° C, more preferably at least 1300 ° C, and most preferably at least 1400 ° C.
  • the cold-formed solid is tempered at a temperature of at least 1250 ° C. for at least one hour, preferably at a temperature of 1400 ° C. for one to three hours.
  • the costs of the process increase with the duration and the annealing temperature.
  • the minimum temperature for the tempering process is 1100 ° C.
  • the maximum temperature for the annealing process is 20 ° C below the melting temperature of the respective dispersion-hardened platinum composition.
  • the temperature treatment or the temperature treatments of the cold-formed volume body are or will be used to heal defects of the bulk body.
  • the cross-sectional area of the volume body is reduced by more than 20% due to the cold forming, the cross-sectional area of the volume body of the dispersion-hardened platinum composition being reduced by a maximum of 20% for each individual cold forming, more preferably at most 18% and more preferably at most 15% is reduced, and between each cold working, a temperature treatment of the cold-formed volume body is carried out at which the cold-worked product is annealed at at least 1100 ° C for at least one hour.
  • each cold forming means that preferably after each cold forming a temperature treatment is carried out at at least 1100 ° C for at least one hour, so that the number of cold forming steps and the number of annealing steps is the same.
  • the implementation of several cold forming and temperature treatments has the advantage that with the relatively easy and inexpensive to perform cold forming and temperature treatments and larger transformations are feasible without that the dispersion-hardened platinum composition is weakened, that is, without, for example, that the alloy is reduced in their creep strength , It has even been surprisingly found that the creep strength increasingly improves with increasing number of forming and annealing steps.
  • the cross-sectional area of the volume body of the dispersion-hardened platinum composition is reduced by at least 5%, preferably reduced by at least 8%, and more preferably reduced by at least 10%.
  • Forming steps involving only a minor reduction in the cross-sectional area of the dispersion-hardened bulk body of less than 5% per forming step and subsequent annealing do not significantly contribute to an improvement in creep rupture strength.
  • the process is also consuming and therefore uneconomical. This is all the more the case, the greater the number of forming steps required in order to achieve the desired final dimension of the dispersion-hardened volume body.
  • a number of 8 forming steps is preferred in order to obtain the desired final size. This number of forming steps is a good compromise between economy and improvement of mechanical properties.
  • the cold worked product is annealed at at least 1550 ° C for at least 24 hours, at least 1600 ° C for at least 12 hours, at least 1650 ° C for at least one hour is annealed or at a temperature of 1690 ° C to 1740 ° C for at least 30 minutes.
  • any dispersion-hardened platinum composition is suitable. Surprising advantages, however, result from the use of semi-finished products, which were generally subjected to hot working.
  • the dispersion-hardened platinum composition may be hot worked at a temperature of at least 800 ° C prior to cold forming, preferably formed at a temperature of at least 1000 ° C, most preferably formed at a temperature of at least 1250 ° C.
  • a further subject matter of the present invention is a process for producing a product from a dispersion-hardened platinum composition, which is characterized in that, prior to providing the dispersion-hardened platinum composition, it consists of a composition of at least 70% by weight of platinum and not more than 29.95% by weight. % of other noble metals, wherein the other precious metals are selected from ruthenium, rhodium, gold, palladium and iridium, and 0.05 wt .-% to 0.5 wt .-% of at least one non-noble metal selected from zirconium, cerium, scandium and Yttrium is prepared by at least partially oxidizing the non-noble metal or the non-noble metals.
  • the non-noble metal or non-noble metals will be at least 70%, preferably at least 90%, reacted to metal oxides.
  • a further subject matter of the present invention is a process for producing a product from a dispersion-hardened platinum composition, which is characterized in that, prior to providing the dispersion-hardened platinum composition, it consists of a composition of at least 70% by weight of platinum and not more than 29.95% by weight. % of other precious metals and from 0.05% to 0.5% by weight of at least one non-noble metal selected from ruthenium, zirconium, cerium, scandium and yttrium is prepared by at least partially oxidizing the non-noble metal or non-noble metals ,
  • the non-noble metal or non-noble metals will be at least 70%, preferably at least 90%, reacted to metal oxides.
  • the treatment of the non-noble metal or the non-noble metals may preferably be carried out at a temperature between 600 ° C and 1600 ° C in an oxidizing atmosphere, preferably between 800 ° C and 1000 ° C in an oxidizing atmosphere.
  • the method of making a product from a dispersion-cured platinum composition may preferably be combined with the previously described method of processing and the embodiments of the invention described herein as preferred.
  • a further subject of the present invention is a dispersion-hardened platinum material obtainable by a method for processing and / or a method for producing a product from a dispersion-hardened platinum composition.
  • This article provides excellent mechanical properties in combination with excellent processability and low cost and inexpensive manufacturability.
  • a cylindrical volume body of the dispersion-hardened platinum material withstands a tensile load of 9 MPa in the direction of the length of the volume at a temperature of 1600 ° C. for at least 40 hours without tearing, preferably withstands at least 50 hours without tearing, particularly preferably withstands at least 100 hours without tearing and / or that a sheet of the dispersion-hardened platinum material having a rectangular cross-section of 0.85 mm by 3.9 mm and a length of 140 mm, in a furnace chamber at 1650 ° C to two parallel cylindrical rods with a circular cross-section and 2 mm diameter are placed at a distance of 100 mm and the sheet in the middle with a weight of 30 g
  • a dispersion-hardened platinum material with the mechanical properties described above for a cylindrical volume body is the subject of the present invention.
  • the dispersion-hardened platinum material 0.05 wt .-% to 0.4 wt .-%, particularly preferably 0.05 wt .-% to 0.3 wt .-% of at least one at least partially oxidized non-noble metal selected from zirconium, cerium, scandium and yttrium.
  • a material with excellent mechanical properties and very good processability can be provided by this embodiment.
  • the dispersion-hardened platinum material may be a sheet, a tube or a wire or a product formed from a wire, tube and / or sheet.
  • a further subject matter of the present invention is a use of a dispersion-hardened platinum material or of a reshaped volume body of a platinum composition obtainable or obtained by a method according to the invention for processing and / or with a method according to the invention for producing a product from a dispersion-hardened platinum composition the glass industry or equipment to be used in a laboratory.
  • the invention is based on the surprising finding that it is possible by the low cold working (with at most 20% change in the cross-sectional area) to enter only such weak structural impairments, such as crystal lattice dislocations in the dispersion-hardened platinum composition that succeeds with the downstream temperature treatment, annealing them again to such an extent that the stability of the reformed platinum composition is significantly higher than in known methods for cold working dispersion-hardened platinum compositions. If stronger transformations are desired, they may be achieved either with an upstream hot working or a series of small cold forming operations are performed sequentially, with annealing of the structural degradation by a thermal treatment being performed between each cold working.
  • the gentle, low cold forming internal damage such as microcracks, delaminations of the particle / matrix interfaces and pores are avoided on grain boundary surfaces, which can not be cured or only with great effort.
  • Particularly damaging are microcracks and pores, which are formed by the deformation on the grain boundaries, since they particularly affect the mechanical stability of the dispersion-hardened platinum composition.
  • the method according to the invention it is possible to avoid these impairments. This has made it possible for the first time to produce a dispersion-hardened platinum composition with very high mechanical stability and excellent processability, in particular weldability, which is likewise claimed according to the invention.
  • Example 1 Based on the in EP 1 964 938 A1 In Example 1, a billet was cast with PtRh10 (alloy of 90 wt.% Pt and 10 wt.% Rh) and 2200 ppm of non-noble metals (1800 ppm Zr and 400 ppm Y). Subsequently, the ingot was treated mechanically and thermally. So this was rolled to a plate thickness of 2.2 mm, then recrystallization annealed and then rolled to a plate thickness of 2 mm. The sheet was then oxidized at 900 ° C for 18 days and then ductile annealed at 1400 ° C for 6 hours.
  • Example 1 Based on the in EP 1 964 938 A1 In Example 1, a billet was cast with PtRh10 (alloy of 90 wt.% Pt and 10 wt.% Rh) and 2200 ppm of non-noble metals (1800 ppm Zr and 400 ppm Y). Subsequently, the ingot was treated mechanically and thermally. So this was rolled to a sheet thickness of 3.3 mm, then recrystallization annealed and then rolled to a plate thickness of 3 mm. The Sheet was then oxidized at 900 ° C for 27 days and then ductile annealed at 1400 ° C for 6 hours.
  • Example 1 Based on the in EP 1 964 938 A1 In Example 1, a billet was cast with PtRh10 (alloy of 90 wt.% Pt and 10 wt.% Rh) and 2120 ppm of non-noble metals (1800 ppm Zr, 270 ppm Y and 50 ppm Sc). Subsequently, the ingot was treated mechanically and thermally. So this was rolled to a sheet thickness of 3.3 mm, then recrystallization annealed and then rolled to a plate thickness of 3 mm. The sheet was then oxidized at 900 ° C for 24 days and then ductile annealed at 1400 ° C for 6 hours.
  • the semifinished product precursor 1 obtained according to the method set out above with a thickness of about 2 mm is further processed according to the invention after the following rolling and annealing steps.
  • the sheet was rolled to 1.7 mm and then annealed at 1400 ° C for 4 h. Thereafter, the sheet is rolled to 1.4 mm and annealed at 1400 ° C for 2 h. Then, further rolled to 1.2 mm and annealed again at 1400 ° C for 2 h. Then it is rolled to 1 mm and annealed again at 1400 ° C. Then it is rolled to the final thickness of 0.85 mm and a final annealing at 1100 ° C for 1 h carried out.
  • the reduction in the cross-sectional area per rolling step is 20%.
  • Example 1 is essentially repeated, but after rolling to a final thickness of 0.85 mm, a final annealing at 1700 ° C for 1 h is performed.
  • the semifinished product precursor 2 obtained according to the method set out above with a thickness of about 3 mm is further processed according to the invention after the following rolling and calcination steps.
  • the sheet was rolled to 2.4 mm and then annealed at 1150 ° C for 4 h. Thereafter, the sheet is rolled to 1.92 mm and annealed at 1150 ° C for 4 h. Then it is rolled to 1.53 mm and again annealed for 4 h at 1150 ° C.
  • the rolling and annealing steps are repeated 3 more times, rolling first to 1.22 mm, then to 0.99 mm and then to 0.8 mm and annealing after each rolling step for 4 h at 1150 ° C.
  • the reduction in the cross-sectional area per rolling step is 20%.
  • the semifinished product precursor 2 obtained according to the method set out above with a thickness of about 3 mm is further processed according to the invention after the following rolling and calcination steps.
  • the sheet was rolled to 2.4 mm and then annealed at 1300 ° C for 4 h. Thereafter, the sheet is rolled to 1.92 mm and annealed at 1300 ° C for 4 h. Then it is rolled to 1.53 mm and annealed again for 4 h at 1300 ° C.
  • the rolling and annealing steps are repeated 3 more times, rolling first to 1.22 mm, then to 0.99 mm and then to 0.8 mm and annealing after each rolling step for 4 h at 1300 ° C.
  • the reduction in the cross-sectional area per rolling step is 20%.
  • the semifinished product precursor 2 obtained according to the method set out above with a thickness of about 3 mm is further processed according to the invention after the following rolling and calcination steps.
  • the sheet was rolled to 2.4 mm and then annealed at 1400 ° C for 4 h. Thereafter, the sheet is rolled to 1.92 mm and annealed at 1400 ° C for 4 h. Then it is rolled to 1.53 mm and again annealed for 4 h at 1400 ° C.
  • the rolling and annealing steps are repeated 3 more times, rolling first to 1.22 mm, then to 0.99 mm and then to 0.8 mm and annealing after each rolling step for 4 h at 1400 ° C.
  • the reduction in the cross-sectional area per rolling step is 20%.
  • the semifinished product precursor 2 obtained according to the method set out above with a thickness of about 3 mm is further processed according to the invention after the following rolling and calcination steps.
  • the sheet was rolled to 2.55 mm and then annealed at 1400 ° C for 4 h. Thereafter, the sheet is rolled to 2.16 mm and annealed at 1400 ° C for 4 h. Then it gets to 1.84 mm rolled and annealed again for 4 h at 1400 ° C.
  • the rolling and annealing steps are repeated 5 more times, rolling first to 1.56 mm, then to 1.33 mm, then to 1.13 mm, then to 0.96 mm and then to 0.8 mm, and after each rolling step for 4 h at 1400 ° C is annealed.
  • the reduction in cross-sectional area per rolling step is 15%.
  • the semifinished product precursor 3 obtained according to the method set out above with a thickness of about 3 mm is further processed according to the invention after the following rolling and calcining steps.
  • the sheet was rolled to 2.4 mm and then annealed at 1150 ° C for 4 h. Thereafter, the sheet is rolled to 1.92 mm and annealed at 1150 ° C for 4 h. Then it is rolled to 1.53 mm and again annealed for 4 h at 1150 ° C.
  • the rolling and annealing steps are repeated 3 more times, rolling first to 1.22 mm, then to 0.99 mm and then to 0.8 mm and annealing after each rolling step for 4 h at 1150 ° C.
  • the reduction in the cross-sectional area per rolling step is 20%.
  • the semifinished product precursor 3 obtained according to the method set out above with a thickness of about 3 mm is further processed according to the invention after the following rolling and calcining steps.
  • the sheet was rolled to 2.55 mm and then annealed at 1400 ° C for 4 h. Thereafter, the sheet is rolled to 2.16 mm and annealed at 1400 ° C for 4 h. Then it is rolled to 1.84 mm and again annealed for 4 h at 1400 ° C.
  • the rolling and annealing steps are repeated 5 more times, rolling first to 1.56 mm, then to 1.33 mm, then to 1.13 mm, then to 0.96 mm and then to 0.8 mm, and after each rolling step for 4 h at 1400 ° C is annealed.
  • the reduction in cross-sectional area per rolling step is 15%.
  • the semifinished product precursor 3 obtained according to the method set out above with a thickness of about 3 mm is further processed according to the invention after the following rolling and calcining steps.
  • the sheet was rolled to 2.7 mm and then annealed at 1400 ° C for 4 h. Thereafter, the sheet is rolled to 2.43 mm and annealed at 1400 ° C for 4 h. Then it is rolled to 2.19 mm and again annealed for 4 h at 1400 ° C.
  • the rolling and annealing steps are repeated 9 more times, first at 1.97 mm, then at 1.77 mm, then at 1.60 mm, then at 1.44 mm, then 1.29 mm, then 1.16 mm, then 1.05 mm, then 0.94 mm and then 0.85 mm, and after each rolling step for 4 h at 1400 ° C is annealed.
  • the reduction in the cross-sectional area per rolling step is 10%.
  • Example 9 is essentially repeated, but after rolling to a final thickness of 0.85 mm, a final annealing at 1700 ° C for 1 h is performed.
  • the semifinished product precursor 3 obtained according to the method set out above with a thickness of about 3 mm is further processed according to the invention after the following rolling and calcining steps.
  • the sheet was rolled at 1100 ° C (hot working) to 1.5 mm and then annealed at 1400 ° C for 4 h. Thereafter, the sheet is rolled to 1.2 mm (1st cold working) and then annealed at 1250 ° C for 4 h. Then rolled 1.02 mm (2nd cold forming) and then again annealed at 1250 ° C for 4 h.
  • the rolling and annealing steps are repeated 3 more times, rolling first to 0.94 mm (3rd cold working), then to 0.86 mm (4th cold working) and then to 0.8 mm (5th cold working), and after each rolling step for 4 h at 1250 ° C is annealed.
  • the reduction in the cross-sectional area is 50% for the hot-forming step, 20% for the cold-forming steps, then 15% and then 8% each.
  • the semifinished product precursor 1 obtained according to the method set out above with a thickness of about 2 mm is further processed according to a conventional method.
  • the sheet is rolled directly to 1 mm and annealed at 1000 ° C. It is then rolled to 0.85 mm and a final annealing at 1000 ° C for 1 h carried out.
  • the semifinished product precursor 2 obtained according to the method set out above with a thickness of about 3 mm is further processed according to a conventional method.
  • the sheet is rolled to 1.5 mm and annealed at 1400 ° C for 4 h. Then it is rolled to 0.8 mm.
  • the reduction in cross-sectional area per rolling step is 50%.
  • the semifinished product precursor 3 obtained according to the method set out above with a thickness of about 3 mm is further processed according to a conventional method.
  • the sheet is rolled to 1.5 mm and annealed at 1400 ° C for 4 h. Then it is rolled to 0.8 mm.
  • the reduction in cross-sectional area per rolling step is 50%.
  • Examples 1, 2, 9, 10 and Comparative Example 1 To measure the creep rupture strength is measured on a sheet sample with a cross section of 0.85 mm ⁇ 3.9 mm and a length of 120 mm (Examples 1, 2, 9, 10 and Comparative Example 1) or 0.8 mm x 3.9 mm and a length of 120 mm (Examples 3, 4, 5, 6, 7, 8, 11 and Comparative Examples 2 and 3) appended a weight corresponding to the desired load in MPa for said cross-section.
  • the sample is brought to temperature by current flow and controlled by pyrometer measurement to the desired temperature.
  • the time to break of the sample is determined and indicates the creep rupture strength.

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Claims (15)

  1. Procédé de traitement d'une composition de platine durcie par dispersion caractérisé par les étapes : de préparation d'un corps volumique d'une composition de platine durcie par dispersion avec au moins 70 % en poids de platine et au maximum 29,95 % en poids d'autres métaux nobles, où les autres métaux nobles sont choisis parmi le ruthénium, le rhodium, l'or, le palladium et l'iridium, ainsi que de 0,05 % en poids à 0,5 % en poids d'au moins un métal non noble au moins partiellement oxydé choisi parmi le zirconium, le cérium, le scandium et l'yttrium ; de transformation à froid de la composition de platine durcie par dispersion, où la surface de la section transversale du corps volumique à base de la composition de platine durcie par dispersion est réduite d'au maximum 20 % lors de la transformation à froid ; et d'exécution ultérieure d'un traitement thermique du corps volumique transformé à froid dans lequel le produit transformé à froid est conditionné thermiquement à au moins 1100 °C pendant au moins une heure.
  2. Procédé selon la revendication 1, caractérisé en ce que la composition de platine durcie par dispersion est transformée avec une transformation thermique à une température d'au moins 800 °C avant la transformation à froid, est transformée de préférence à une température d'au moins 1000 °C, de manière particulièrement préférée, est transformée à une température d'au moins 1250 °C.
  3. Procédé selon la revendication 1 ou la revendication 2, caractérisé en ce que plusieurs transformations à froid sont exécutées les unes après les autres et la surface de la section transversale du corps volumique est réduite de plus de 20 % par les transformations à froid, où la surface de la section transversale du corps volumique à base de la composition de platine durcie par dispersion est réduite d'au maximum 20 % lors de chaque transformation à froid individuelle et un traitement thermique du corps volumique transformé à froid est effectué entre chaque transformation à froid, dans lequel le produit transformé à froid est conditionné thermiquement à au moins 1100 °C pour au moins une heure.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que, lors du dernier traitement thermique après la dernière transformation à froid du corps volumique, le produit transformé à froid est conditionné thermiquement à au moins 1550 °C pour au moins 24 h, à au moins 1600 °C pour au moins 12 heures, à au moins 1650 °C pour au moins une heure ou est conditionné thermiquement à une température de 1690 °C à 1740 °C pour au moins 30 minutes.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que, lors de la transformation à froid, un fil est tiré ou pressé, où, lors de la transformation à froid, la surface de la section transversale du fil à base de la composition de platine durcie par dispersion est réduite au maximum de 20 %, ou une tôle est laminée, étirée, pressée ou comprimée lors de la transformation à froid, où, lors de la transformation à froid, la surface de la section transversale de la tôle ou l'épaisseur de la tôle à base de la composition de platine durcie par dispersion est réduite au maximum de 20 %, ou un tube est laminé, étiré ou pressé lors de la transformation à froid, où la surface de la section transversale du tube à base de la composition de platine durcie par dispersion est réduite au maximum de 20 % lors de la transformation à froid.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que la transformation à froid est effectuée à une température de 500 °C ou moins.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que le traitement thermique ou les traitements thermiques du corps volumique transformé à froid est ou sont employé(s) pour réparer des défauts du corps volumique.
  8. Procédé selon l'une des revendications précédentes, caractérisé en ce que, lors du traitement thermique, le corps volumique transformé à froid est conditionné thermiquement à une température d'au moins 1250 °C pour au moins une heure, de préférence, à une température de 1400 °C pour une à trois heures.
  9. Procédé de fabrication d'un produit à partir d'une composition de platine durcie par dispersion avec un procédé selon l'une des revendications précédentes, caractérisé en ce qu'avant la préparation de la composition de platine durcie par dispersion, celle-ci est fabriquée à partir d'une composition à base d'au moins 70 % en poids de platine et au maximum 29,95 % en poids d'autres métaux nobles, les autres métaux nobles étant choisis parmi le ruthénium, le rhodium, l'or, le palladium et l'iridium, ainsi que de 0,05 % en poids à 0,5 % en poids d'au moins un métal non noble parmi le zirconium, le cérium, le scandium et l'yttrium par une oxydation au moins partielle du métal non noble ou des métaux non nobles.
  10. Procédé selon la revendication 9, caractérisé en ce que le traitement du métal non noble ou des métaux non nobles a lieu à une température entre 600 °C et 1600 °C dans une atmosphère oxydante, a lieu de préférence entre 800 °C et 1000 °C dans une atmosphère oxydante.
  11. Matériau en platine durci par dispersion caractérisé en ce que le matériau en platine durci par dispersion peut être obtenu avec un procédé selon l'une des revendications 1 à 8 ou avec un procédé selon la revendication 9 ou la revendication 10, caractérisé en ce qu'un corps volumique cylindrique à base du matériau en platine durci par dispersion résiste sans rupture à une sollicitation en traction de 9 MPa dans le sens de la longueur du corps volumique à une température de 1600 °C au moins pendant 40 heures, et/ou qu'une tôle à base du matériau en platine durci par dispersion avec une section transversale rectangulaire de 0,85 mm par 3,9 mm et une longueur de 140 mm, qui est déposée dans une enceinte de four à 1650 °C sur deux tiges cylindriques disposées parallèlement avec une section transversale circulaire et avec 2 mm de diamètre à une distance de 100 mm et que la tôle est soumise au centre à un poids de 30 g, a subi une courbure inférieure à 40 mm en 40 heures.
  12. Matériau en platine durci par dispersion selon la revendication 11, caractérisé en ce qu'un corps volumique cylindrique à base du matériau en platine durci par dispersion résiste sans rupture à une sollicitation en traction de 9 MPa dans le sens de la longueur du corps volumique à une température de 1600 °C au moins pendant 50 heures, de manière particulièrement préférée, résiste sans rupture au moins 100 heures, et/ou qu'une tôle à base du matériau en platine durci par dispersion avec une section transversale rectangulaire de 0,85 mm par 3,9 mm et une longueur de 140 mm, qui est déposée dans une enceinte de four à 1650 °C sur deux tiges cylindriques disposées parallèlement avec une section transversale circulaire et avec 2 mm de diamètre à une distance de 100 mm et que la tôle est soumise au centre à un poids de 30 g, a subi une courbure inférieure à 30 mm en 40 heures, de manière particulièrement préférée, a subi une courbure inférieure à 20 mm, idéalement, a subi une courbure inférieure à 14 mm.
  13. Matériau en platine durci par dispersion selon la revendication 11 ou la revendication 12, caractérisé en ce que le matériau en platine durci par dispersion est une tôle, un tube ou un fil ou est un produit formé à partir d'un fil, d'un tube et/ou d'une tôle.
  14. Matériau en platine durci par dispersion selon l'une des revendications 11 à 13, caractérisé en ce que le matériau en platine durci par dispersion comprend 0,05 % en poids à 0,3 % en poids d'au moins un métal non noble au moins partiellement oxydé choisi parmi le zirconium, le cérium, le scandium et l'yttrium.
  15. Utilisation d'un matériau en platine durci par dispersion selon l'une des revendications 11 à 14 ou d'un matériau en platine durci par dispersion fabriqué avec le procédé selon les revendications 1 à 8, ou d'un matériau en platine durci par dispersion fabriqué selon la revendication 9 ou la revendication 10 pour des appareils utilisables dans l'industrie du verre ou dans un laboratoire.
EP14812166.8A 2013-12-06 2014-12-04 Procédé d'usinage d'un matériau à base de platine renforcé par dispersion Active EP3077556B1 (fr)

Applications Claiming Priority (2)

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DE102013225187.4A DE102013225187B4 (de) 2013-12-06 2013-12-06 Verfahren zur Bearbeitung einer dispersionsgehärteten Platinzusammensetzung
PCT/EP2014/076600 WO2015082630A1 (fr) 2013-12-06 2014-12-04 Procédé de traitement de compositions de platines durcies par dispersion

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EP3077556B1 true EP3077556B1 (fr) 2019-06-19

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EP (1) EP3077556B1 (fr)
JP (1) JP6530402B2 (fr)
KR (1) KR101831090B1 (fr)
CN (1) CN105765092B (fr)
DE (1) DE102013225187B4 (fr)
WO (1) WO2015082630A1 (fr)

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CN108165812B (zh) * 2017-11-16 2019-09-24 重庆材料研究院有限公司 一种用于铂基器皿的弥散强化型材料及其制备方法和应用
EP3971311B1 (fr) * 2020-09-17 2022-07-06 Heraeus Deutschland GmbH & Co. KG Alliage de métaux précieux durci par dispersion amélioré
EP3978884B1 (fr) 2020-10-02 2024-05-29 Heraeus Precious Metals GmbH & Co. KG Fil ayant une composition platine permettant de mettre en contact des capteurs de température
EP4282526A1 (fr) 2022-05-25 2023-11-29 Heraeus Deutschland GmbH & Co. KG Réseau catalytique doté d'un fil en métal précieux à partir d'un alliage de métal précieux renforcé par phase dispersée

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WO2015082630A1 (fr) 2015-06-11
DE102013225187B4 (de) 2018-07-19
JP6530402B2 (ja) 2019-06-12
JP2017502170A (ja) 2017-01-19
CN105765092B (zh) 2018-10-19
KR20160097249A (ko) 2016-08-17
CN105765092A (zh) 2016-07-13
DE102013225187A1 (de) 2015-06-11
US20160289808A1 (en) 2016-10-06
KR101831090B1 (ko) 2018-02-21
EP3077556A1 (fr) 2016-10-12

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