JP2017502170A - Method for processing a dispersion strengthened platinum composition - Google Patents

Abstract

The invention relates to at least 70% by weight of platinum and up to 29.95% by weight of other noble metals and 0.05% of at least partially oxidized base metal selected from zirconium, cerium, scandium and yttrium. A volume of dispersion-strengthened platinum composition containing mass% to 0.5 mass% is prepared, and the prepared volume of dispersion-strengthened platinum composition is cold-molded. Reducing the cross-sectional area of the volume of platinum composition by up to 20% and subsequently subjecting the cold-formed volume to heat treatment, wherein the cold-formed product is at least 1100 ° C. at least The present invention relates to a method of processing a dispersion strengthened platinum composition that is annealed for 1 hour. Furthermore, the present invention describes a method for producing a product comprising a dispersion strengthened platinum composition, as well as a dispersion strengthened platinum material obtained by the processing method described above. Furthermore, the use of a dispersion strengthened platinum material is described.

Description

  The present invention relates to a method of processing a dispersion strengthened platinum composition. Furthermore, the present invention relates to a method for producing a product from a dispersion strengthened platinum composition. The invention further relates to the product obtained by the above-described method and the use of such a platinum composition.

  Formed bodies made of platinum are used in many ways in high temperature processes, in which case the material must exhibit high corrosion resistance. For example, platinum components such as stirrers or glass fiber bushings which are mechanically loaded are used in the glass industry. However, the disadvantage of platinum as a material is that the mechanical strength at high temperatures is low. Therefore, dispersion strengthened platinum compositions are generally used for the high temperature processes described above.

  The production and processing of this material is known, for example, from documents GB 1 340 076 A, GB 2 082 205 A, EP 0 683 240 A2, EP 1 188 844 A1 and EP 1 964 938 A1.

  In order to manufacture a member made of a dispersion strengthened platinum composition, generally, a hot-rolled ingot is first prepared. The resulting semi-finished product can subsequently be cold formed.

  By molding at low temperature, it is possible to adapt to each set value at low cost. However, it has been confirmed that the mechanical properties of the dispersion-strengthened platinum material are still not good enough, or at least there is room for improvement, especially in such a molding technique. These components must be replaced more frequently than is desired or used for some applications. This exchange is associated with high costs. However, molding at high temperatures (so-called hot forming) is very expensive and difficult because the machines required for this are very expensive.

  The object of the present invention is therefore to overcome the drawbacks of the prior art. In particular, this method should enable low-cost applications of parts made of platinum compositions with respect to individual requirements while improving mechanical properties. At the same time, the resulting member should exhibit a long service time and as low wear as possible. Furthermore, this method is preferably simple and can be implemented at low cost. Furthermore, the molded member preferably exhibits good workability, particularly weldability.

The subject of the present invention is a process:
At least 70% by weight of platinum and up to 29.95% by weight of other noble metals and 0.05% by weight of at least one partially oxidized base metal selected from zirconium, cerium, scandium and yttrium Providing a volume of dispersion strengthened platinum composition (Volumenkoerper) having ˜0.5% by weight;
A step of cold forming the dispersion strengthened platinum composition and reducing the cross-sectional area of the volume of the dispersion strengthened platinum composition by up to 20% during the cold forming; and This is solved by a method of processing a dispersion strengthened platinum composition characterized by the step of tempering the cold-formed product at least 1100 ° C. for at least 1 hour.

  The cross-sectional area in the sense of the present invention is taken to be the area of the surface formed during the (imaginary) cutting of the volume body. The plane extending from this cross section may be perpendicular or nearly perpendicular to the longest spreading direction of the volume, but need not be perpendicular.

  The above-mentioned mass percentages are 100% in total. In this case, the mass of the base metal is based on the mass of the metal.

  Preferably, the one or more base metals are at least 70%, preferably at least 90% oxidized with oxygen. In this case, since all oxidation states of the base metal are taken into account, preferably a maximum of 30 atomic%, particularly preferably a maximum of 10 atomic% of the base metal is present as metal, ie in the formal oxidation state 0.

  Preferably, the at least partially oxidized base metal in the dispersion strengthened platinum composition is 0.05% to 0.5% by weight, particularly preferably 0.1% to 0.4% by weight, in particular Preferably 0.15 mass%-0.3 mass% is contained.

  Due to the high proportion of base metal oxide, the service life of this volume at mechanical loads is improved. A volume having a low base metal oxide ratio has advantages with respect to the workability of the volume, such as weldability.

  In the method of the present invention, a volume is prepared. This concept of volume is interpreted comprehensively in this case. Preferably, the volume may be configured, for example, in the form of a plate, tube or wire.

  The three-dimensional extent of the volume is not particularly limited in this case and can be selected according to requirements. Thus, for example, the prepared plate material, tube material or wire material can have a thickness in the range of 0.1 mm to 10 mm, preferably 0.3 to 5 mm. This thickness here represents the smallest extent of the volume. In the case of wire, this is the diameter, and in the case of pipe, it is the difference between the outer radius and the inner radius, which is also referred to as the wall thickness of the tube.

  The platinum composition that can be used in the present invention comprises at least 70% by weight of platinum and up to 29.95% by weight of other noble metals. The composition is therefore mainly composed of platinum and the at least partially oxidized base metal described above. The platinum material may be pure platinum, excluding ordinary impurities, and at least partially oxidized base metal is mixed therein. Furthermore, the platinum composition may contain other noble metals, where the platinum composition is in this case a platinum alloy.

  In the case of the present invention, it may be envisaged that the other noble metal is selected from ruthenium, rhodium, gold, palladium and iridium.

  The prepared volume is cold formed by the method according to the invention. The concept of “cold forming” is known in the field, where the forming takes place at a relatively low temperature below the recrystallization temperature of the platinum composition and in particular is drawn, compressed, deep drawn, cold Includes rolling, cold forging and pressing. This shaping involves deformation over a large area of the volume. Preferably, this volume is intended to be deformed over at least 50%, particularly preferably at least 75%, particularly preferably at least 95% of its volume. If this volume is, for example, a plate, then preferably at least 50%, particularly preferably at least 75%, particularly preferably at least 95% of the surface of the plate is exposed to force or pressure, for example rolled. . In the case of a wire rod, this surface is simplified and can be based on a plane perpendicular to the smallest extent (thickness) of the volume. If this volume is, for example, a wire or tube, preferably at least 50%, particularly preferably at least 75%, particularly preferably at least 95% of the length of the wire or tube is exposed to force, for example drawn. The

  In the present invention, it is important that only a relatively small amount of molding is performed during cold forming. Preferably, the cross-sectional area of the volume consisting of this dispersion strengthened platinum composition is reduced by a maximum of 20%, particularly preferably by a maximum of 18% and very particularly preferably by a maximum of 15%. This value relates to the cross-sectional area of the volume that is reduced to the maximum. In the case of a plate that is only rolled in one direction, the reduced cross-sectional area results from, for example, the thickness of the volume as well as the unstretched spread. In the case of wire or tubing, the reduction in cross-sectional area results from changes in diameter or wall thickness. Since the volume of this volume does not change with molding, at least one cross-sectional area must be enlarged during this molding. In the case of a plate material, a tube material, or a wire material, for example, the length increases at the time of forming, so that the area in the direction in which the length increases increases. The direction in which the deformation force acts is particularly parallel or perpendicular to the plane extending from the cross section.

  In a preferred embodiment, with this cold forming, the cross-sectional area of the volume composed of the dispersion strengthened platinum composition is reduced by at least 5%, preferably by at least 8%, particularly preferably by at least 10%. Is scheduled.

  It was confirmed that the internal damage of the dispersion-strengthened volume essentially does not contribute to the improvement of creep resistance during forming and subsequent annealing with a cross-sectional area reduction of less than 5% each. The smaller the change in the cross-sectional area per molding step, the smaller the cross-sectional area is within the above range, which is accompanied by a reduction of the cross-sectional area of 5% to 20%, preferably 8% to 18%, particularly preferably 10% to 15%. Compared to molding, the effect on improving creep resistance is also less.

  Furthermore, the wire is drawn or compressed by cold forming, where the cross-sectional area of the wire comprising the dispersion-strengthened platinum composition by this cold forming is up to 20%, preferably up to 18%, particularly preferably up to 15%. Reducing or rolling, drawing, compressing or pressing the plate in cold forming, where the cold cross-section of the plate made of dispersion strengthened platinum composition or the thickness of the plate is up to 20%, Preferably by a maximum of 18%, particularly preferably by a maximum of 15%, or by cold forming, the tube is rolled, drawn or compressed, wherein in this cold forming the cross-sectional area of the tube composed of a dispersion strengthened platinum composition, A reduction of up to 20%, preferably up to 18%, particularly preferably up to 15% may be planned.

  In the case of the present invention, cold forming does not produce microcracks or pores inside the dispersion strengthened platinum composition, or produces less than 100 microcracks and / or less than 1000 pores per cubic millimeter. May be scheduled.

  After the cold forming of the volume, heat treatment of the cold formed volume is performed, wherein the cold formed product is tempered at least 1100 ° C. for at least 1 hour. This tempering can preferably take place over a period of at least 90 minutes, in particular at least 120 minutes, particularly preferably at least 150 minutes, particularly preferably at least 180 minutes. The temperature at which this tempering is carried out can preferably be at least 1200 ° C., particularly preferably at least 1250 ° C., particularly preferably at least 1300 ° C., more particularly preferably at least 1400 ° C.

  Furthermore, during the heat treatment of the cold-formed volume body, it may be tempered to temper at a temperature of at least 1250 ° C. for at least 1 hour, preferably at a temperature of 1400 ° C. for 1 to 3 hours. .

  The longer the tempering process and the higher the temperature at which the heat treatment is performed, the better the mechanical properties of the cold-formed volume. However, at some point the improvement in mechanical properties becomes saturated and there is a significant grain growth risk, which again deteriorates the mechanical properties. Furthermore, the cost of this method increases with time and temperature. The minimum temperature for the tempering operation is 1100 ° C. The maximum temperature for the tempering operation is 20 ° C. below the melting temperature of the respective dispersion strengthened platinum composition.

  Preferably, one or more heat treatments of the cold formed volume may be scheduled to be applied to recover defects in the volume.

  In the case of the method according to the invention, a plurality of cold forming operations are carried out in succession and the cold forming reduces the cross-sectional area of the volume by more than 20%, in which case the individual cold forming operations are carried out. Then, the cross-sectional area of the volume made of the dispersion strengthened platinum composition is reduced by up to 20%, preferably up to 18%, particularly preferably up to 15%, and the cold-formed volume between each cold-forming. It may be scheduled to perform the heat treatment and to temper the cold-formed product during the heat treatment at least 1100 ° C. for at least 1 hour.

  Here, “between each cold forming” means that the heat treatment is preferably carried out at least 1100 ° C. for at least 1 hour after each cold forming, so the number of cold forming steps and the number of tempering steps are the same. It means that.

  Multiple cold forming and heat treatments can be performed without weakening the dispersion strengthened platinum composition, i.e., the alloy should be relatively easy and inexpensive to perform, for example, without reducing its creep resistance. There is an advantage that relatively large deformation can be realized even by hot forming and heat treatment. On the contrary, it has been surprisingly found that creep resistance is improved in an increasing direction as the number of forming and tempering steps increases.

  In the case of a preferred embodiment of the present invention, it is preferable that the cross-sectional area of the volume composed of the dispersion-strengthened platinum composition is reduced by at least 5% for each cold forming continuously in a plurality of cold forming operations. Is expected to be reduced by at least 8%, particularly preferably by at least 10%.

  A molding process that involves a slight reduction of less than 5% of the cross-sectional area of the dispersion-strengthened volume and subsequent tempering per molding process does not contribute essentially to improved creep resistance. Compared with molding with a reduction of the cross-sectional area of 5% to 20%, the effect on the improvement of creep resistance is more if the change of the cross-sectional area per molding process becomes small within the above-mentioned range. It becomes a little. With multiple alternating alternating molding and tempering steps, this method is even more expensive and thereby uneconomical. This is even more true as the number of molding steps required to achieve the desired final dimensions of the dispersion enhanced volume increases. In order to obtain the desired final dimensions, a number of 8 molding steps is preferred. This number of deformation steps is a favorable compromise between economy and improved mechanical properties.

  Preferably, during the final heat treatment after the last cold forming of the volume, the cold formed product is at least 1550 ° C for at least 24 hours, at least 1600 ° C for at least 12 hours, 1650 ° C for at least 1 Temporary tempering or tempering at a temperature between 1690 ° C and 1749 ° C for at least 30 minutes can be scheduled.

  By this last step, the simple defects to be recovered of the dispersion strengthened platinum composition are almost eliminated in its final form, and the product thus produced thereby exhibits very high creep resistance.

  All dispersion strengthened platinum compositions are suitable as starting products for this processing method. However, surprising advantages generally arise from the use of semi-finished products that have been exposed to hot forming. The dispersion strengthened platinum composition is formed by hot forming at a temperature of at least 800 ° C., preferably at a temperature of at least 1000 ° C., particularly preferably at a temperature of at least 1250 ° C., before cold forming. be able to.

  Another subject of the present invention is selected from at least 70% by weight of platinum and up to 29.95% by weight of other noble metals and ruthenium, zirconium, cerium, scandium and yttrium prior to the preparation of the dispersion strengthened platinum composition. Characterized in that the dispersion strengthened platinum composition is produced from a composition comprising 0.05% by mass to 0.5% by mass of at least one base metal by at least partial oxidation of the one or more base metals. A method for producing a product comprising a dispersion-strengthened platinum composition.

  Preferably, at least 70%, preferably at least 90% of the one or more base metals are reacted to the metal oxide.

  The treatment of the one or more base metals can be performed preferably at a temperature of 600 ° C. to 1600 ° C. in an oxidizing atmosphere, and preferably at a temperature of 800 ° C. to 1000 ° C. in an oxidizing atmosphere.

  The method of producing a product comprising a dispersion strengthened platinum composition may preferably be combined with the processing method described above and its embodiments described as preferred therein.

  Another subject of the present invention is a dispersion-strengthened platinum material obtained by a processing method and / or a method for producing a product comprising a dispersion-strengthened platinum composition. This subject provides excellent mechanical properties combined with excellent processability or low cost and hassle-free manufacturability.

  Preferably, the cylindrical volume of dispersion strengthened platinum material withstands a tensile load of 9 MPa in the length direction of the volume at a temperature of 1600 ° C. without tearing for at least 40 hours, preferably for at least 50 hours. A plate of 0.85 mm × 3.9 mm rectangular cross section and 140 mm length made of dispersion-strengthened platinum material, particularly preferably without tearing for at least 100 hours. When mounted on two cylindrical rods having a circular cross section of 2 mm in diameter and arranged in parallel at intervals of 100 mm at 1650 ° C., and a load of 30 g is applied to the center of the plate Further, the deflection after 40 hours is less than 40 mm, preferably less than 30 mm, particularly preferably less than 20 mm, and still more preferably Deflection may be expected to be less than 14mm.

  A cylindrical volume is in the context of the present invention interpreted as a shaped body resembling a straight cylindrical shape, in particular a cylindrical shape or a shaped body resembling a cylindrical shape with a non-circular or non-round base. . The cylindrical volume body is also a rectangular body having a side length in the range of 0.5 mm to 5 mm (that is, a molded body similar to a columnar shape having a rectangular bottom surface).

  The length of the cylindrical volume is interpreted as the longest spread. The direction of this length is the axis of a cylindrical volume body in the case of a wire or tube, and is the spread of the plane of this plate in the case of a plate.

  Furthermore, dispersion-strengthened platinum materials having the mechanical properties described above for cylindrical volumes are the subject of the present invention.

  Preferably, the dispersion strengthened platinum material is 0.05% to 0.4% by weight, particularly preferably 0.8% by weight, of at least one partially oxidized base metal selected from zirconium, cerium, scandium and yttrium. It may be planned to contain 05 mass% to 0.3 mass%. According to this aspect, it is possible to provide a material having particularly excellent mechanical properties and extremely good workability.

  In a particular embodiment, the dispersion strengthened platinum material can be a plate, tube or wire, or a product formed from a wire, tube and / or plate.

  Other subjects of the invention are obtained by the processing method according to the invention and / or by the manufacturing method according to the invention of products from dispersion strengthened platinum compositions for equipment to be used in the glass industry or in the laboratory. Or use of a volume formed from the dispersion-strengthened platinum material or platinum composition obtained.

  The present invention reinforces the stability of the shaped platinum composition with subsequent cold treatment, with a slight cold forming (with a change in cross-sectional area of up to 20%), the known cold of the dispersion strengthened platinum composition. It is based on the surprising finding that structural damage, such as crystal lattice defects, that is weak enough to achieve a significantly higher recovery than in the case of the forming method can be achieved. If stronger forming is desired, this forming can be achieved by preceding hot forming, or several slight cold formings can be carried out in succession, where structurally between each cold forming. Damage recovery is performed by heat treatment. As a finding within the scope of the present invention, mechanical weakening of cold formed dispersion strengthened platinum compositions is due to strong defects such as microcracks, particle / matrix interface delamination and too many pores at grain boundaries. And the cause of these defects was found to be too high degree of deformation or too much reduction in cross-sectional area.

  In particular, such as microcracks, particle / matrix interface delamination and pores at the grain interface that cannot be recovered with great effort due to mild, slight cold forming Internal damage is reduced. In particular, microcracks and pores that occur at grain boundaries due to molding are detrimental because they particularly impair the mechanical stability of the dispersion strengthened platinum composition. This damage suppression is achieved by the method according to the invention. Thereby, for the first time, it has been successful to produce a dispersion-strengthened platinum composition having very high mechanical stability and excellent workability, in particular weldability, which is likewise claimed by the present invention.

  The following examples illustrate further embodiments of the present invention, but are not intended to limit the present invention.

Semi-finished product precursor 1
Manufacture of a semi-finished product precursor with a thickness of 2 mm by internal oxidation with Zr and Y
According to the method described in Example 1 of EP 1 964 938 A1, an ingot having PtRh10 (alloy consisting of 90% by mass of Pt and 10% by mass of Rh) and 2200 ppm of base metal (Zr1800 ppm and Y400 ppm) was cast. Subsequently, the ingot was processed mechanically and thermally. Thus, this ingot was rolled to a thickness of 2.2 mm, then annealed for recrystallization, and subsequently rolled to a plate pressure of 2 mm. This plate was then oxidized at 900 ° C. for 18 days and subsequently ductile annealed at 1400 ° C. for 6 hours.

Semi-finished product precursor 2
Manufacture of a semi-finished product precursor with a thickness of 3 mm by internal oxidation with Zr and Y
According to the method described in Example 1 of EP 1 964 938 A1, an ingot having PtRh10 (alloy consisting of 90% by mass of Pt and 10% by mass of Rh) and 2200 ppm of base metal (Zr1800 ppm and Y400 ppm) was cast. Subsequently, the ingot was processed mechanically and thermally. Thus, this ingot was rolled to a thickness of 3.3 mm, then annealed for recrystallization, and subsequently rolled to a plate pressure of 3 mm. This plate was then oxidized at 900 ° C. for 27 days and subsequently ductile annealed at 1400 ° C. for 6 hours.

Semi-finished product precursor 3
Manufacture of a half-finished product precursor with a thickness of 3 mm by internal oxidation with Zr, Y and Sc
According to the method described in Example 1 of EP 1 964 938 A1, an ingot having PtRh10 (alloy consisting of 90% by mass of Pt and 10% by mass of Rh) and 2120 ppm of base metal (Zr1800 ppm, Y270 ppm and Sc50 ppm) was cast. Subsequently, the ingot was processed mechanically and thermally. Thus, this ingot was rolled to a thickness of 3.3 mm, then annealed for recrystallization, and subsequently rolled to a plate pressure of 3 mm. The plate was then oxidized at 900 ° C. for 24 days and subsequently ductile annealed at 1400 ° C. for 6 hours.

Example 1
The semi-finished product precursor 1 having a thickness of about 2 mm obtained by the above method is subsequently processed by the following rolling and annealing processes according to the present invention.

  This plate was rolled to 1.7 mm and subsequently annealed at 1400 ° C. for 4 hours. Thereafter, the plate is rolled to 1.4 mm and annealed at 1400 ° C. for 2 hours. Next, it is further rolled to 1.2 mm and newly annealed at 1400 ° C. for 2 hours. Subsequently, it rolls to 1 mm and anneals again at 1400 degreeC. Then, it rolls to the final thickness of 0.85 mm, and final annealing is implemented at 1100 degreeC for 1 hour. The reduction rate of the cross-sectional area for each rolling process is 20%.

Example 2
Example 1 is almost repeated, but after rolling to a final thickness of 0.85 mm, a final annealing is performed at 1700 ° C. for 1 hour.

Example 3
The semi-finished product precursor 2 having a thickness of about 3 mm obtained by the above method is subsequently processed by the following rolling and annealing processes according to the present invention.

  This plate was rolled to 2.4 mm and subsequently annealed at 1150 ° C. for 4 hours. Thereafter, this plate material is rolled to 1.92 mm and annealed at 1150 ° C. for 4 hours. Subsequently, it rolls to 1.53 mm and anneals again at 1150 degreeC for 4 hours. The rolling process and the annealing process are repeated three more times. At this time, the film is initially rolled to 1.22 mm, then 0.99 mm, and then 0.8 mm, and annealed at 1150 ° C. for 4 hours after each rolling process. The reduction rate of the cross-sectional area for each rolling process is 20%.

Example 4
The semi-finished product precursor 2 having a thickness of about 3 mm obtained by the above method is subsequently processed by the following rolling and annealing processes according to the present invention.

  This plate was rolled to 2.4 mm and subsequently annealed at 1300 ° C. for 4 hours. Thereafter, this plate material is rolled to 1.92 mm and annealed at 1300 ° C. for 4 hours. Subsequently, it rolls to 1.53 mm and anneals again at 1300 degreeC for 4 hours. The rolling process and the annealing process are repeated three more times. At this time, the film is initially rolled to 1.22 mm, then 0.99 mm, and then 0.8 mm, and annealed at 1300 ° C. for 4 hours after each rolling process. The reduction rate of the cross-sectional area for each rolling process is 20%.

Example 5
The semi-finished product precursor 2 having a thickness of about 3 mm obtained by the above method is subsequently processed by the following rolling and annealing processes according to the present invention.

  This plate was rolled to 2.4 mm and subsequently annealed at 1400 ° C. for 4 hours. Thereafter, this plate material is rolled to 1.92 mm and annealed at 1400 ° C. for 4 hours. Next, it is rolled to 1.53 mm and annealed again at 1400 ° C. for 4 hours. The rolling process and the annealing process are repeated three more times. At this time, the film is initially rolled to 1.22 mm, then to 0.99 mm, and subsequently to 0.8 mm, and annealed at 1400 ° C. for 4 hours after each rolling process. The reduction rate of the cross-sectional area for each rolling process is 20%.

Example 6
The semi-finished product precursor 2 having a thickness of about 3 mm obtained by the above method is subsequently processed by the following rolling and annealing processes according to the present invention.

  This plate was rolled to 2.55 mm and subsequently annealed at 1400 ° C. for 4 hours. Thereafter, the plate is rolled to 2.16 mm and annealed at 1400 ° C. for 4 hours. Next, it is rolled to 1.84 mm and annealed again at 1400 ° C. for 4 hours. The rolling and annealing steps were repeated five more times, initially rolling 1.56 mm, then 1.33 mm, then 1.13 mm, then 0.96 mm and then 0.8 mm, after each rolling step 1400 Annealing at 4 ° C. for 4 hours. The reduction rate of the cross-sectional area for each rolling process is 15%.

Example 7
The semi-finished product precursor 3 having a thickness of about 3 mm obtained by the above-described method is subsequently processed by the following rolling and annealing processes according to the present invention.

  This plate was rolled to 2.4 mm and subsequently annealed at 1150 ° C. for 4 hours. Thereafter, this plate material is rolled to 1.92 mm and annealed at 1150 ° C. for 4 hours. Subsequently, it rolls to 1.53 mm and anneals again at 1150 degreeC for 4 hours. The rolling process and the annealing process are repeated three more times. At this time, the film is initially rolled to 1.22 mm, then 0.99 mm, and then 0.8 mm, and annealed at 1150 ° C. for 4 hours after each rolling process. The reduction rate of the cross-sectional area for each rolling process is 20%.

Example 8
The semi-finished product precursor 3 having a thickness of about 3 mm obtained by the above-described method is subsequently processed by the following rolling and annealing processes according to the present invention.

  This plate was rolled to 2.55 mm and subsequently annealed at 1400 ° C. for 4 hours. Thereafter, the plate is rolled to 2.16 mm and annealed at 1400 ° C. for 4 hours. Next, it is rolled to 1.84 mm and annealed again at 1400 ° C. for 4 hours. The rolling and annealing steps were repeated five more times, initially rolling 1.56 mm, then 1.33 mm, then 1.13 mm, then 0.96 mm and then 0.8 mm, after each rolling step 1400 Annealing at 4 ° C. for 4 hours. The reduction rate of the cross-sectional area for each rolling process is 15%.

Example 9
The semi-finished product precursor 3 having a thickness of about 3 mm obtained by the above-described method is subsequently processed by the following rolling and annealing processes according to the present invention.

  This plate was rolled to 2.7 mm and subsequently annealed at 1400 ° C. for 4 hours. Thereafter, this plate material is rolled to 2.43 mm and annealed at 1400 ° C. for 4 hours. Subsequently, it rolled to 2.19 mm and again annealed at 1400 degreeC for 4 hours. The rolling and annealing steps were repeated nine more times, initially 1.97 mm, then 1.77 mm, then 1.60 mm, then 1.44 mm, then 1.29 mm, then 1.16 mm, then 1.05 mm, It is then rolled to 0.94 mm and subsequently to 0.85 mm and annealed at 1400 ° C. for 4 hours after each rolling step. The reduction rate of the cross-sectional area for each rolling process is 10%.

Example 10
Example 9 is almost repeated, but after rolling to a final thickness of 0.85 mm, a final annealing is performed at 1700 ° C. for 1 hour.

Example 11
The semi-finished product precursor 3 having a thickness of about 3 mm obtained by the above-described method is subsequently processed by the following rolling and annealing processes according to the present invention.

  This plate material was rolled to 1.5 mm at 1100 ° C. (hot forming) and subsequently annealed at 1400 ° C. for 4 hours. Thereafter, this plate material is rolled to 1.2 mm (first cold forming) and subsequently annealed at 1250 ° C. for 4 hours. Next, it is rolled to 1.02 mm (second cold forming) and subsequently annealed at 1250 ° C. for 4 hours. The rolling process and the annealing process are repeated three times. At this time, initially 0.94 mm (third cold forming), then 0.86 mm (fourth cold forming), and then 0.8 mm (fifth Cold forming) and annealed at 1250 ° C. for 4 hours after each rolling step. The reduction ratio of the cross-sectional area is 50% in the hot forming process, 20% in the cold forming process, then 15%, and then 8% each.

Comparative Example 1
The semi-finished product precursor 1 having a thickness of about 2 mm obtained by the above method is subsequently processed by a usual method. For this reason, this plate material is directly rolled to 1 mm and annealed at 1000 ° C. Then, it rolls to 0.85 mm and final annealing is implemented at 1000 degreeC for 1 hour.

Comparative Example 2
The semi-finished product precursor 2 having a thickness of about 3 mm obtained by the above-described method is subsequently processed by a usual method. Therefore, this plate material is rolled to 1.5 mm and annealed at 1400 ° C. for 4 hours. Then, it rolls to 0.8 mm. The reduction rate of the cross-sectional area for each rolling process is 50%.

Comparative Example 3
The semi-finished product precursor 3 having a thickness of about 3 mm obtained by the above-described method is subsequently processed by a usual method. Therefore, this plate material is rolled to 1.5 mm and annealed at 1400 ° C. for 4 hours. Then, it rolls to 0.8 mm. The reduction rate of the cross-sectional area for each rolling process is 50%.

Mechanical properties of the obtained platinum material Creep resistance by destructive test For the measurement of creep resistance, a plate material sample of 0.85 mm × 3.9 mm cross section and 120 mm length (Examples 1, 2, 9, 10 and Comparative Example 1) or 0.8 mm × 3.9 mm cross section and 120 mm long plate material samples (Examples 3, 4, 5, 6, 7, 8, 11 and Comparative Examples 2 and 3), A weight corresponding to a desired load indicated by MPa is applied to the above-described cross section. The sample is heated by an electric current and adjusted to a desired temperature by pyrometer measurement. Determines the time until the sample breaks and indicates creep resistance.

Table 1: Creep resistance until breakage at a load of 1600 ° C and 9 MPa

Creep resistance by flex test Another method for evaluating creep resistance is the flex test. For this purpose, a plate material having a cross section of 0.85 mm × 10 mm and a length of 140 mm (Examples 1, 2, 9, 10 and Comparative Example 1) or a plate material having a cross section of 0.8 mm × 10 mm and a length of 140 mm (Examples 3, 4, 5, 6, 7, 8, 11 and Comparative Examples 2 and 3) were placed on two parallel ceramic rods with a spacing of 100 mm, and the center was loaded with a weight of 30 g. . This sample configuration was heated to 1650 ° C. in a chamber furnace and the deflection of the sample was measured after 40 hours.

Table 2: Creep resistance by deflection test

  The embodiments described above can achieve an unexpected improvement in mechanical properties by the measures according to the invention, wherein this improvement is further enhanced by an annealing process at temperatures above 1100 ° C., in particular at temperatures above 1500 ° C. Show what you can do.

  The features of the invention disclosed in the above specification, in the claims and in the examples are intended to enable the implementation of the invention in the case of various embodiments of the invention, either individually or independently. It can also be important as a combination.

Claims (15)

Next step:
At least 70% by weight of platinum and up to 29.95% by weight of other noble metals, and a base metal selected from zirconium, cerium, scandium and yttrium, at least partially oxidized at least one base metal being Preparing a volume of a dispersion strengthened platinum composition containing 05 mass% to 0.5 mass%,
Cold forming the dispersion strengthened platinum composition, wherein during the cold forming, the cross-sectional area of the volume of the dispersion strengthened platinum composition is reduced by up to 20%, and subsequently
A step of heat-treating the cold-formed volume, wherein the cold-formed product is tempered at least at 1100 ° C. for at least 1 hour during the heat treatment. how to.   Prior to the cold forming, the dispersion strengthened platinum composition is formed by hot forming at a temperature of at least 800 ° C, preferably at a temperature of at least 1000 ° C, particularly preferably at a temperature of at least 1250 ° C. The method according to claim 1, wherein:   A plurality of cold forming operations are carried out successively, and the cross-sectional area of the volume body is reduced by more than 20% by the plurality of cold forming operations. The cross-sectional area of the volume body made of a dispersion strengthened platinum composition is reduced by up to 20%, and during each cold forming, the cold-formed volume body is subjected to heat treatment, and during the heat treatment, the cold body is cooled. The method according to claim 1 or 2, characterized in that the inter-molded product is tempered at least 1100 ° C for at least 1 hour.   During the final heat treatment after the last cold forming of the volume, the cold formed product is subjected to 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 1 4. Process according to any one of claims 1 to 3, characterized in that it is tempered for a period of time or tempered for at least 30 minutes at a temperature of 1690C to 1740C.   The wire is drawn or compressed by cold forming, and the cross-sectional area of the wire made of the dispersion strengthened platinum composition is reduced by up to 20% by the cold forming, or the plate is rolled and drawn by cold forming. Processing, compression processing or pressure processing, reducing the cross-sectional area of the plate material made of the dispersion strengthened platinum composition or the thickness of the plate material by up to 20% by the cold forming, or rolling the tube material by cold forming In the case of drawing or compressing, the cold forming reduces the cross-sectional area of the pipe material made of the dispersion strengthened platinum composition by up to 20%, according to any one of claims 1 to 4. The method described.   The method according to claim 1, wherein the cold forming is performed at a temperature of 500 ° C. or less.   The method according to any one of claims 1 to 6, characterized in that the one or more heat treatments of the cold-formed volume are applied for the recovery of defects in the volume. .   The tempering of the cold-formed volume is tempered at a temperature of at least 1250 ° C for at least 1 hour, preferably tempered at a temperature of 1400 ° C for 1-3 hours. The method according to any one of the above.   9. A method for producing a product comprising a dispersion strengthened platinum composition according to any one of claims 1 to 8, wherein at least 70% by weight of platinum and other noble metals are prepared prior to preparation of the dispersion strengthened platinum composition. A composition comprising a maximum of 29.95% by weight and at least one base metal selected from ruthenium, zirconium, cerium, scandium and yttrium from 0.05% by weight to 0.5% by weight. A method for producing a product comprising a dispersion-strengthened platinum composition, comprising producing the dispersion-strengthened platinum composition by at least partial oxidation.   The treatment of the one or more base metals is performed in an oxidizing atmosphere at a temperature of 600 ° C to 1600 ° C, preferably in an oxidizing atmosphere at a temperature of 800 ° C to 1000 ° C. the method of.   Dispersion strengthened platinum material, wherein the dispersion strengthened platinum material is obtained by a method according to any one of claims 1 to 8 or obtained by a method according to claim 9 or 10. Reinforced platinum material.   The cylindrical volume made of the dispersion strengthened platinum material can withstand at a temperature of 1600 ° C. with a tensile load of 9 MPa in the length direction of the volume body for at least 40 hours, preferably at least 50 hours. A plate material having a rectangular cross section of 0.85 mm × 3.9 mm and a length of 140 mm made of the dispersion strengthened platinum material, particularly preferably withstanding without tearing for at least 100 hours, At 1650 ° C., placed on two circular rods with a circular cross-section and a diameter of 2 mm arranged in parallel at intervals of 100 mm, and the center of the plate is loaded with a weight of 30 g In addition, the deflection after 40 hours is less than 40 mm, preferably less than 30 mm, particularly preferably less than 20 mm, more particularly preferred. Ku is characterized in that the deflection is less than 14 mm, the dispersion strengthened platinum material according to claim 11.   The dispersion-strengthened platinum material according to claim 11 or 12, wherein the dispersion-strengthened platinum material is a plate, a tube, or a wire, or a product formed from a wire, a tube, and / or a plate.   The dispersion-strengthened platinum material contains 0.05% by mass to 0.3% by mass of at least one base metal selected from zirconium, cerium, scandium, and yttrium, which is at least partially oxidized. The dispersion strengthened platinum material according to any one of claims 11 to 13.   15. A dispersion strengthened platinum material according to any one of claims 11 to 14 or a method according to any one of claims 1 to 8 for equipment to be used in the glass industry or in the laboratory. Use of a processed dispersion strengthened platinum material or a dispersion strengthened platinum material produced by the method according to claim 9 or 10.