EP2281905A1 - Stability improvement of iridium, rhodium and their alloys - Google Patents

Stability improvement of iridium, rhodium and their alloys Download PDF

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EP2281905A1
EP2281905A1 EP20100005962 EP10005962A EP2281905A1 EP 2281905 A1 EP2281905 A1 EP 2281905A1 EP 20100005962 EP20100005962 EP 20100005962 EP 10005962 A EP10005962 A EP 10005962A EP 2281905 A1 EP2281905 A1 EP 2281905A1
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iridium
alloys
rhodium
calcium
boron
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French (fr)
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EP2281905B1 (en
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Uwe Hortig
Verena Baier
Harald Manhardt
Oliver Dr. Warkentin
David Francis Prof. Dr. Lupton
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Heraeus Deutschland GmbH and Co KG
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WC Heraus GmbH and Co KG
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    • 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
    • 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

Definitions

  • the invention relates to iridium and its Zr and Hf-free alloys and rhodium and its Zr and Hf-free alloys with high creep rupture strength at high temperatures.
  • Iridium as one of the platinum group metals is used, for example, in crucibles for growing single crystals of refractory oxide melts, e.g. from Nd: YAG laser crystals, or used in components for the glass industry.
  • crucibles for growing single crystals of refractory oxide melts, e.g. from Nd: YAG laser crystals, or used in components for the glass industry.
  • a high creep and creep rupture strength of the iridium at high temperatures is of crucial importance.
  • tungsten and / or zirconium-containing iridium alloys are described for high temperature applications which additionally contain from 0.01 to 0.5% by weight of further elements such as molybdenum and hafnium and optionally ruthenium at from 0.01 to 10% by weight.
  • JP 56-81646 A Platinum-based jewelery alloys containing calcium boride or boron for increasing strength, especially hardness, after high temperature treatment such as brazing, are described.
  • the object of the present invention is the creep rupture strength of iridium at high Temperature while maintaining the ductility and processability of the material to increase, without using the said elements. It is accordingly advantageous if the material in question is also free of titanium.
  • the creep strength of the iridium doped in this way increases by 20 to 30% at a temperature of 1800 ° C. in comparison to undoped iridium by the addition of calcium and boron in the range of a few ppm. It is expected that this will also be achieved for iridium alloys as well as rhodium and its alloys.
  • the service lives are in a range of 1403.7 h (about 58.5 days) at 6.7 MPa to 0.73 h at 25 MPa and decrease with increasing voltage. As the strain rate increases with increasing stress, the elongations at break do not show a significant tendency.
  • Table 2 Values from the creep rupture curve of the undoped lr batch Lifetime [h] Creep rupture strength [MPa] Strain rate [s -1 ] 10 16.9 6.5 ⁇ 10 -6 100 11.0 5.6 x 10 -7 1000 7.2 4.9 ⁇ 10 -8
  • the iridium ingot was then forged analogously to the undoped iridium batch in the comparative example and rolled to a final thickness of 1 mm.

Abstract

Iridium or rhodium and its zirconium- and hafnium-free alloys further comprising 0.5-30 ppm of boron and 0.5-20 ppm of calcium, is claimed : An independent claim is included for a method for increasing the creep strength of iridium and/or rhodium or its/their alloys comprising adding boron and calcium to the metals or their zirconium- and hafnium-free alloys.

Description

Die Erfindung betrifft Iridium und dessen Zr- und Hf-freie Legierungen sowie Rhodium und dessen Zr- und Hf-freie Legierungen mit hoher Zeitstandfestigkeit bei hohen Temperaturen.The invention relates to iridium and its Zr and Hf-free alloys and rhodium and its Zr and Hf-free alloys with high creep rupture strength at high temperatures.

Hintergrund und AufgabenstellungBackground and task

Iridium als eines der Metalle der Platingruppe wird beispielsweise in Tiegeln zur Züchtung von Einkristallen hochschmelzender oxidischer Schmelzen, z.B. von Nd:YAG-Laserkristallen, oder in Bauteilen für die Glasindustrie eingesetzt. Für diese Anwendungen sind neben der Korrosionsbeständigkeit gegenüber oxidischen Schmelzen eine hohe Kriech- und Zeitstandfestigkeit des Iridiums bei hohen Temperaturen von entscheidender Bedeutung.Iridium as one of the platinum group metals is used, for example, in crucibles for growing single crystals of refractory oxide melts, e.g. from Nd: YAG laser crystals, or used in components for the glass industry. For these applications, in addition to the corrosion resistance to oxidic melts, a high creep and creep rupture strength of the iridium at high temperatures is of crucial importance.

Eine Methode zur Erhöhung der Kriech- und Zeitstandfestigkeit von Iridium-Legierungen wird in DE 10 2005 032 591 A1 beschrieben. Es erfolgt eine Dotierung mit Molybdän, Hafnium und gegebenenfalls Rhenium, wobei die Summe aus Molybdän und Hafnium zwischen 0,002 und 1,2 Gew% beträgt (dadurch konnte die Standzeit im Vergleich zu undotiertem Iridium bei einer Belastung von 16,9 MPa auf über das Doppelte gesteigert werden.)One method of increasing the creep and creep rupture strength of iridium alloys is described in US Pat DE 10 2005 032 591 A1 described. It is doped with molybdenum, hafnium and optionally rhenium, wherein the sum of molybdenum and hafnium between 0.002 and 1.2% by weight (thereby the service life compared to undoped iridium at a load of 16.9 MPa to more than double be increased.)

In WO 2004/007782 A1 werden Wolfram und/oder Zirkonium enthaltende Iridium-Legierungen für Hochtemperaturanwendungen beschrieben, die zusätzlich 0,01 bis 0,5 Gew% an weiteren Elementen wie Molybdän und Hafnium enthalten und ggf. Ruthenium mit 0,01 bis 10 Gew%.In WO 2004/007782 A1 For example, tungsten and / or zirconium-containing iridium alloys are described for high temperature applications which additionally contain from 0.01 to 0.5% by weight of further elements such as molybdenum and hafnium and optionally ruthenium at from 0.01 to 10% by weight.

In JP 56-81646 A werden Schmucklegierungen auf Platinbasis beschrieben, die Calciumborid oder Bor zur Erhöhung der Festigkeit, vor allem der Härte, nach einer Hochtemperaturbehandlung, wie z.B. Löten, enthalten.In JP 56-81646 A Platinum-based jewelery alloys containing calcium boride or boron for increasing strength, especially hardness, after high temperature treatment such as brazing, are described.

Bei der Züchtung von einigen hochreinen Laserkristallen sind die vierwertigen Elemente Zr und Hf in den lridium-Tiegeln nicht erwünscht, da sie zu Verunreinigungen in der Kristallschmelze führen können, welche die Lasereigenschaften im späteren Einsatz beeinträchtigen. Deshalb liegt die Aufgabe der vorliegenden Erfindung darin, die Zeitstandfestigkeit des Iridiums bei hoher Temperatur unter Beibehaltung der Duktilität und Verarbeitbarkeit des Materials zu erhöhen, ohne die genannten Elemente zu verwenden. Es ist entsprechend von Vorteil, wenn das betreffende Material auch frei von Titan ist.In the growth of some high purity laser crystals, the tetravalent elements Zr and Hf in the iridium crucibles are undesirable because they can lead to impurities in the crystal melt which interfere with the laser properties in later use. Therefore, the object of the present invention is the creep rupture strength of iridium at high Temperature while maintaining the ductility and processability of the material to increase, without using the said elements. It is accordingly advantageous if the material in question is also free of titanium.

Überraschenderweise wurde gefunden, dass sich durch die Zugabe von Kalzium und Bor im Bereich von wenigen ppm die Zeitstandfestigkeit des auf diese Weise dotierten Iridiums bei einer Temperatur von 1800 °C im Vergleich zu undotiertem Iridium um 20 bis 30 % erhöht. Es ist davon auszugehen, dass dies auch für Iridiumlegierungen sowie Rhodium und seine Legierungen erreicht wird.Surprisingly, it has been found that the creep strength of the iridium doped in this way increases by 20 to 30% at a temperature of 1800 ° C. in comparison to undoped iridium by the addition of calcium and boron in the range of a few ppm. It is expected that this will also be achieved for iridium alloys as well as rhodium and its alloys.

Die folgenden Beispiele erläutern die Erfindung näher. Teile- und Prozentangaben beziehen sich wie in der übrigen Beschreibung auf das Gewicht, sofern nicht anders angegeben.The following examples illustrate the invention in more detail. Parts and percentages are by weight unless otherwise indicated, as in the remainder of the description.

Vergieichsbeispiel:Vergieichsbeispiel:

8 kg Iridium wurden in einem ZrO2-Tiegel aufgeschmolzen und in eine wassergekühlte Kupferkokille abgegossen. Der Iridium-Barren wurde anschließend bei 1600 bis 1700°C geschmiedet und in mehreren Schritten auf eine Enddicke von 1 mm gewalzt. Vor und zwischen den jeweiligen Walzstichen wurde der Barren bzw. das Blech auf 1400 °C erhitzt. Das Blech wies eine Härte von HV10 = 270 auf. Aus dem gewalzten Blech wurden Proben für Zeitstandversuche entnommen.8 kg of iridium were melted in a ZrO 2 crucible and poured into a water-cooled copper mold. The iridium ingot was then forged at 1600 to 1700 ° C and rolled in several steps to a final thickness of 1 mm. Before and between the respective rolling passes, the billet or sheet was heated to 1400 ° C. The sheet had a hardness of HV10 = 270. Samples for creep tests were taken from the rolled sheet.

Für die auf diese Weise hergestellte Iridium-Charge wurde in Zeitstandversuchen bei einer Temperatur von 1800 °C eine Zeitstandkurve aufgenommen. Dabei wurden die Standzeiten bei angelegten Spannungen zwischen 6,7 und 25 MPa ermittelt und die Werte anschließend durch eine Kurve angenähert. Die Messergebnisse sind in Tabelle 1 zusammengefasst. Tabelle 1: Ergebnisse der Zeitstandversuche an reinem Iridium (ohne Dotierung mit Kalzium und Bor) Spannung [MPa] Standzeit [h] Bruchdehnung [%] Dehnrate [s-1] 6,7 1403,7 18,2 3,2 · 10-8 8,3 385,9 22,3 1,2 · 10-7 9,5 225,0 23,9 2,6 · 10-7 10 95,0 36,9 6,4 · 10-7 13 56,8 50,0 9,4 · 10-7 16 17,48 22,4 1,6 · 10-6 18 10,1 > 50 1,4 · 10-5 21 4,38 98,8 2,7 · 10-5 23 1,67 13,5 1,5 · 10-5 25 0,73 59,8 2,0 · 10-4 For the iridium batch thus prepared, a creep rupture curve was recorded in creep tests at a temperature of 1800 ° C. The service lives at applied voltages between 6.7 and 25 MPa were determined and the values were then approximated by a curve. The measurement results are summarized in Table 1. TABLE 1 Results of the creep tests on pure iridium (without doping with calcium and boron) Voltage [MPa] Lifetime [h] Elongation at break [%] Strain rate [s -1 ] 6.7 1,403.7 18.2 3.2 · 10 -8 8.3 385.9 22.3 1,2 · 10 -7 9.5 225.0 23.9 2.6 · 10 -7 10 95.0 36.9 6.4 · 10 -7 13 56.8 50.0 9.4 · 10 -7 16 17.48 22.4 1.6 · 10 -6 18 10.1 > 50 1.4 · 10 -5 21 4.38 98.8 2.7 · 10 -5 23 1.67 13.5 1.5 · 10 -5 25 0.73 59.8 2.0 · 10 -4

Die Standzeiten bewegen sich in einem Bereich von 1403,7 h (ca. 58,5 Tage) bei 6,7 MPa bis 0,73 h bei 25 MPa und sinken mit zunehmender Spannung. Während die Dehnrate mit steigender Spannung zunimmt, zeigen die Bruchdehnungen keine signifikante Tendenz.The service lives are in a range of 1403.7 h (about 58.5 days) at 6.7 MPa to 0.73 h at 25 MPa and decrease with increasing voltage. As the strain rate increases with increasing stress, the elongations at break do not show a significant tendency.

Aus der ermittelten Zeitstandkurve ergeben sich für vorgegebene Standzeiten folgende interpolierte Werte für die Zeitstandfestigkeit: Tabelle 2: Werte aus der Zeitstandkurve der undotierten lr-Charge Standzeit [h] Zeitstandfestigkeit [MPa] Dehnrate [s-1] 10 16,9 6,5 · 10-6 100 11,0 5,6 · 10-7 1000 7,2 4,9 · 10-8 From the creep rupture curve determined, the following interpolated values for the creep rupture strength result for given service lives: Table 2: Values from the creep rupture curve of the undoped lr batch Lifetime [h] Creep rupture strength [MPa] Strain rate [s -1 ] 10 16.9 6.5 · 10 -6 100 11.0 5.6 x 10 -7 1000 7.2 4.9 · 10 -8

1. Ausführungsbeispiel:1st embodiment:

8 kg Iridium wurden in einem ZrO2-Tiegel aufgeschmolzen und in eine wassergekühlte Kupferkokille abgegossen. Kurz vor dem Abguss wurde eine mit ca. 0,08 g (10 ppm) Kalzium und 0,08 g (10 ppm) Bor gefüllte Tasche aus Pt-Folie (20 mm x 20 mm x 0,05 mm) in die Schmelze gegeben.8 kg of iridium were melted in a ZrO 2 crucible and poured into a water-cooled copper mold. Shortly before the casting, a pocket of Pt foil (20mm x 20mm x 0.05mm) filled with approximately 0.08g (10ppm) of calcium and 0.08g (10ppm) of boron was added to the melt ,

Der Iridium-Barren wurde anschließend analog zur undotierten Iridium-Charge im Vergleichsbeispiel geschmiedet und auf eine Enddicke von 1 mm gewalzt. Die Härte der Bleche lag zwischen HV10 = 226 und 242. Aus dem gewalzten Blech wurden Proben für Zeitstandversuche und Analysen entnommen.The iridium ingot was then forged analogously to the undoped iridium batch in the comparative example and rolled to a final thickness of 1 mm. The hardness of the sheets was between HV10 = 226 and 242. Samples for creep tests and analyzes were taken from the rolled sheet.

Auf diese Weise wurden insgesamt sieben Chargen Iridium hergestellt und untersucht. Mithilfe von GDL-Analysen (Glow Discharge Lamp) wurden zunächst die Gehalte an Kalzium und Bor bestimmt. Die Analyse-Ergebnisse sind in Tabelle 3 aufgeführt. Der Gehalt an Kalzium und Bor ist für alle Chargen nahezu identisch. Tabelle 3: Ergebnisse der GDL-Analysen: Ca- und B-Gehalte der dotierten Ir-Chargen Charge Gehalt an Ca [ppm] Gehalt an B [ppm] A - - B - - C 4 3 D 4 3 E 4 3 F 4 3 G 5 3 In this way, a total of seven batches of iridium were produced and investigated. Using GDL ( G low D ischarge L amp) analyzes, the levels of calcium and boron were initially determined certainly. The analysis results are shown in Table 3. The content of calcium and boron is almost identical for all batches. Table 3: Results of GDL analyzes: Ca and B contents of the doped Ir batches charge Content of Ca [ppm] Content of B [ppm] A - - B - - C 4 3 D 4 3 e 4 3 F 4 3 G 5 3

Ausgehend von der Zeitstandkurve der undotierten Iridium-Charge wurden Zeitstandversuche bei einer Temperatur von 1800 °C und einer angelegten Spannung von 16,9 MPa durchgeführt. Im Vergleich zur Standzeit der undotierten Iridium-Charge von 10 h (Tabelle 2) wurden für die dotierten Chargen deutlich höhere Standzeiten von 17,93 bis zu 56,52 h erreicht (Tabelle 4).Based on the creep rupture of the undoped iridium batch, creep rupture tests were carried out at a temperature of 1800 ° C. and an applied stress of 16.9 MPa. Compared to the service life of the undoped iridium charge of 10 h (Table 2), significantly longer service lives of 17.93 to 56.52 h were achieved for the doped charges (Table 4).

Neben dem Anstieg der Standzeiten konnte außerdem eine tendenzielle Zunahme der Bruchdehnungen im Vergleich zum undotierten Iridium beobachtet werden. Der Minimalwert der gemessenen Bruchdehnungen liegt bei 23 %, während ein Maximalwert von 73 % erreicht wurde. Die Dehnraten der dotierten Iridium-Chargen liegen zwischen 8,3 10-7 und 3,4·10-6 s-1. Tabelle 4: Ergebnisse der Zeitstandversuche bei 1800 °C und einer Spannung von 16,9 MPa Charge Standzeiten [h] Bruchdehnung [%] Dehnrate [s-1] A 32,85 55 2,7 · 10-6 45,39 51 1,5 · 10-6 33,47 44 1,2 · 10-6 B 22,48 51 2,2 · 10-6 17,93 68 2,2 · 10-6 19,30 64 3,4 · 10-6 C 50,65 65 1,3 · 10-6 38,66 48 1,2 · 10-6 56,52 73 1,0 · 10-6 D 29,94 73 2,0 · 10-6 18,88 56 2,2 · 10-6 42,67 29 9,8 · 10-7 E 54,89 46 8,3 · 10-7 29,03 23 1,0 · 10-7 34,89 35 1,2 · 10-6 F 53,79 56 9,0 · 10-7 35,66 39 1,1 · 10-6 29,32 45 1,5 · 10-6 G 19,31 57 2.1 · 10-6 47,02 35 7,1 · 10-7 43,83 38 1,2 · 10-6 In addition to the increase in service life, there was also a tendency for elongation at break compared to undoped iridium. The minimum value of the measured elongations at break is 23%, while a maximum value of 73% has been reached. The strain rates of the doped iridium batches are between 8.3 · 10 -7 and 3.4 · 10 -6 s -1 . Table 4: Results of the creep tests at 1800 ° C and a tension of 16.9 MPa charge Lifetime [h] Elongation at break [%] Strain rate [s -1 ] A 32.85 55 2.7 · 10 -6 45.39 51 1.5 · 10 -6 33.47 44 1.2 · 10 -6 B 22.48 51 2.2 · 10 -6 17.93 68 2.2 · 10 -6 19.30 64 3.4 · 10 -6 C 50.65 65 1.3 · 10 -6 38.66 48 1.2 · 10 -6 56.52 73 1.0 · 10 -6 D 29.94 73 2.0 · 10 -6 18.88 56 2.2 · 10 -6 42.67 29 9.8 · 10 -7 e 54.89 46 8.3 · 10 -7 29.03 23 1.0 · 10 -7 34.89 35 1.2 · 10 -6 F 53.79 56 9.0 · 10 -7 35.66 39 1.1 · 10 -6 29.32 45 1.5 · 10 -6 G 19.31 57 2.1 · 10 -6 47.02 35 7.1 · 10 -7 43.83 38 1.2 · 10 -6

2. Ausführungsbeispiel2nd embodiment

Für die Charge F aus dem 1. Ausführungsbeispiel wurde bei einer Temperatur von 1800 °C zusätzlich zu dem Zeitstandversuch bei 16,9 MPa eine Zeitbruchlinie aufgenommen. Die angelegten Spannungen bewegten sich dabei in einem Bereich zwischen 14 MPa und 25 MPa. Die Ergebnisse sind in Tabelle 5 aufgeführt. Tabelle 5: Ergebnisse der Zeitstandversuche bei verschiedenen Spannungen Spannung [MPa] Standzeit [h] Bruchdehnung [%] Dehnrate [s-1] 14,0 95,53 28 2,6 · 10-7 16,9 39,59 47 1,2 · 10-6 18,5 21,71 75 1,5 · 10-6 20,0 14,43 69 2,4 · 10-6 23,0 8,81 69 9,0 · 10-6 25,0 3,44 76 1,7 · 10-5 For the batch F from the 1st embodiment, a time-break line was recorded at a temperature of 1800 ° C. in addition to the creep test at 16.9 MPa. The applied voltages moved in a range between 14 MPa and 25 MPa. The results are shown in Table 5. Table 5: Results of the creep tests at different voltages Voltage [MPa] Lifetime [h] Elongation at break [%] Strain rate [s -1 ] 14.0 95.53 28 2.6 · 10 -7 16.9 39.59 47 1.2 · 10 -6 18.5 21.71 75 1.5 · 10 -6 20.0 14.43 69 2.4 · 10 -6 23.0 8.81 69 9.0 · 10 -6 25.0 3.44 76 1.7x10 -5

Nach Ermittlung der Zeitbruchlinie ergaben sich für vorgegebene Standzeiten folgende interpolierte Zeitstandfestigkeitswerte: Tabelle 6: Werte aus der Zeitstandkurve der mit Kalzium und Bor dotierten Ir-Charge Standzeit [h] Zeitstandfestigkeit [MPa] Dehnrate [s-1] 10 21,3 5,0 · 10-6 100 14,3 3,1 · 10-7 1000 9,5 1,8 · 10-8 After determining the time break line, the following interpolated creep rupture strength values were obtained for specified service lives: Table 6: Values from the creep curve of the calcium and boron-doped Ir charge Lifetime [h] Creep rupture strength [MPa] Strain rate [s -1 ] 10 21.3 5.0 · 10 -6 100 14.3 3.1 · 10 -7 1000 9.5 1.8 · 10 -8

Bei Vergleich dieser Festigkeitswerte mit denen von reinem Iridium bei gleichen Standzeiten wird bei allen Standzeiten eine Erhöhung der Zeitstandfestigkeit von mindestens 23 % erreicht. Die Dehnraten der interpolierten Werte liegen vor allem bei den geringeren Spannungen deutlich unter denen des reinen Iridiums. Bezüglich der gemessenen Bruchdehnungen werden teilweise fast dreifach höhere Werte erreicht als bei reinem Iridium.By comparing these strength values with those of pure iridium with the same service lives, an increase in the creep rupture strength of at least 23% is achieved for all service lives. The strain rates of the interpolated values are significantly lower than those of pure iridium, especially at lower voltages. With regard to the measured elongations at break, in some cases almost three times higher values are achieved than with pure iridium.

Claims (4)

Iridium und dessen Zr- und Hf-freie Legierungen, Rhodium und dessen Zr- und Hf-freie Legierungen, zusätzlich enthaltend 0,5 bis 30 ppm Bor und 0,5 bis 20 ppm Kalzium.Iridium and its Zr and Hf-free alloys, rhodium and its Zr and Hf-free alloys, additionally containing 0.5 to 30 ppm of boron and 0.5 to 20 ppm of calcium. Verfahren zum Erhöhen der Zeitstandfestigkeit von Iridium und dessen Legierungen sowie von Rhodium und dessen Legierungen, dadurch gekennzeichnet, dass den Metallen oder deren Zr- und Hf-freien Legierungen Bor und Calcium zugesetzt werden.Method for increasing the creep rupture strength of iridium and its alloys and of rhodium and its alloys, characterized in that boron and calcium are added to the metals or their Zr and Hf-free alloys. Verwendung von Kalzium und Bor zum Erhöhen der Zeitstandfestigkeit von Iridium und dessen Zr- und Hf-freien Legierungen sowie von Rhodium und dessen Zr- und Hf-freien Legierungen.Use of calcium and boron to increase the creep rupture strength of iridium and its Zr and Hf-free alloys as well as rhodium and its Zr and Hf-free alloys. Verfahren oder Verwendung nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass 0,5 bis 30 ppm Bor und 0,5 bis 20 ppm Kalzium zugesetzt werden.Method or use according to one of the preceding claims, characterized in that 0.5 to 30 ppm boron and 0.5 to 20 ppm calcium are added.
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DE102009031168A1 (en) 2010-12-30

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