US3622310A - Process of preparing noble metal materials having improved high temperature strength properties - Google Patents

Process of preparing noble metal materials having improved high temperature strength properties Download PDF

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Publication number
US3622310A
US3622310A US792110*A US3622310DA US3622310A US 3622310 A US3622310 A US 3622310A US 3622310D A US3622310D A US 3622310DA US 3622310 A US3622310 A US 3622310A
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platinum
percent
process according
noble metal
zirconium
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Expired - Lifetime
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US792110*A
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English (en)
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Gerhard Reinacher
Gerhard Zwingmann
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Evonik Operations GmbH
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Degussa GmbH
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Priority claimed from DE19681608255 external-priority patent/DE1608255A1/de
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    • 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
    • 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

Definitions

  • alloys of one or more of platinum and platinum metals for example rhodium, or gold, with elements having an affinity for oxygen, especially zirconium, are capable of internal oxidation, i.e., they become oxidized not only on the grain boundaries but also in the interior of the grain, if the initial material is subjected to an annealing at a temperature between 800 and l,200,C. for over 5 hours in air or an oxygen containing atmosphere.
  • the maximum time of annealing is not critical but normally is not over 500 hours.
  • the initial material a powder of the alloy, however, it is also possible to subject shaped parts or semifinished products directly to a corresponding treatment.
  • lt is especially advantageous to carry out the heat treatment in two steps.
  • an annealing treatment at a temperature between 300 and 800 C. is carried out for 5 to 500 hours and in the second step an oxidation treatment at a temperature between 800 and l,400 C. is carried out for 0.5 to 50 hours.
  • an oxidation treatment at a temperature between 800 and l,400 C. is carried out for 0.5 to 50 hours.
  • FIGURE of the drawings is a graph of tensile strength of platinum and platinum alloys against time at l,400
  • the process according to the invention is not limited to platinum and its alloys with other noble metals.
  • palladium and palladium alloys can be dispersion strengthened with other noble metals.
  • metals and alloys of such metals of the platinum group including rhodium, ruthenium, iridium and osmium. Even gold and its alloys is hardenable by the method of the invention, although in this case the described effect is not quite as high as with the platinum metals.
  • the content of palladium, rhodium, or the like can be 1 to 49 percent.
  • the named noble metal alloys there are suited not only zirconium but also other elements whose oxides exhibit a high heat of formation. Examples of such elements are aluminum, beryllium, titanium, hafnium, tantalum, and the like. As previously set forth zirconium is preferred.
  • the content of the added metal can be between 0.1 and 5 percent, preferably between 0.5 and 2 percent.
  • a shortening of the annealing time can be accomplished by oxidation under elevated oxygen pressure.
  • the internal oxidation of alloys according to the invention can also take place directly on sheets or wires as well as on powders of the corresponding alloys in order to shorten the oxidation time.
  • the powder is produced, for example by spraying a melt, by flame spraying a wire, or by size reduction through the taking off of shavings.
  • the grain size is 5 to 500 my.
  • EXAMPLE 2 A cast ingot of each of the alloys containing zirconium identified in example 1 was cut on a lathe. The turnings obtained were treated in the same manner as in example 1 and worked to wires of 1 mm. diameter by hot rolling at 1,200 C. and finally with cold drawing. After an annealing for 1 hour at 1,400" C. in air they had the following tensile strengths at room temperature, (a) Pt, 1% Zr, 48 kg./mm. (b) Pt, 9.5% Pd, 1% Zr, 45 kg./mm.” and (c) Pt, 10% Rh, 1% Zr 65 kg./mm.
  • EXAMPLE 3 The alloys of platinum with 1 percent zirconium and platinum with 10 percent rhodium and 1 percent zirconium were melted, homogenized for 2 hours at l,100 C. in a vacuum of 10" torr and processed by filling to a powder. The powder was kept at 700 C. in air for 100 hours followed by annealing with oxidation for 10 hours at l,000 C. in air. Rods were compressed from these materials, sintered and hot and cold worked to wires of 1 mm. diameter. Time to rupture tests at l,400 C. in air were carried out with these materials. The results are shown in the single figure of the drawings in which both the time and tensile strength values are measured on logarithmic scales. The straight line graphs are as follows:
  • the alloys according to the invention are superior to all the comparison materials in two respects. Firstly for a required time to rupture the stress tolerated is generally higher than with the comparison materials of which (3) gives the best previously known values. Secondly the slope of the straight line for the samples accord ing to the invention is substantially smaller than that for the comparison materials. This means that the alloys of the invention behave better in comparison to the other samples, the longer the time required to rupture.
  • the 100 hour time strength for alloys l and (2) ofthe invention are 5.2 and 3.6 kg./mm. respectively, for (3) only 1.1 kg./mm., for (4) only 0.54 kgjmm. while (5) loses all of its strength long before the 100 hours is up (actually at less than hours).
  • the improvement of alloys l and (2) of the invention in comparison with (4) is about tenfold and sevenfold respectively and in comparison to (3) is about fivefold and threefold respectively.
  • the numerical values (in the same sequence) are (l) 3.5, (2) 2.8, (3) 0.32 and (4) 0.1 15 kgJcm. This is an improvement of (l) and (2) in comparison with (4) of over 30 times and 24 times respectively and in comparison with (3) of l 1 times and 9 times respectively.
  • EXAMPLE 4 A sheet of 1 mm. thickness of an alloy of platinum with 1 percent zirconium was annealed at l,000 C. in air. After that the sheet showed the following hardness values:
  • a sheet of unalloyed platinum showed after the same annealing process a hardness value of 50 kg./mm.
  • EXAMPLE 5 A filing powder of an alloy of platinum with 1 percent zirconium was kept at 700 C. a) in air, b) in oxygen at 1 at, c) in oxygen at 5 at for 50 hours followed by annealing with oxidation for 16 hours at 1,000 C. in air. The hardness was a) kg./mm. b) kg./mm. and c) kg./mm.”.
  • EXAMPLE 6 A filing powder of alloys of platinum with 1 percent aluminum and of platinum with 1 percent tantalum was kept at 700C. for 142 hours in air, followed b'y annealing of oxidation for 16 hours at l,000 C. in air. The hardness was for Pt/Al 160 kg./mm. and for Pt/Ta 150 kg./mm. The same nonoxidized alloys showed a hardness of95 and -1 l0 kg./mm.
  • a process of preparing an internally oxidized dispersion hardened noble metal selected from the group consisting of platinum metals and fold and mixtures thereof alloyed with an element having an affinity for oxygen selected from the group consisting of zirconium, aluminum, beryllium, titanium, hafnium, and tantalum comprising subjecting the initial material to a stepwise treatment including a pretreatment at 300-800 C. followed by treatment with an oxygen containing atmosphere at a temperature of 800 C. to 1400 C. for a time sufficient to improve the high temperature strength of the noble metal.
  • a process according to claim 1 wherein the annealing treatment is in an oxygen containing atmosphere at 800 to 1200 C. for at least 5 hours and the element having an affinity for oxygen is present in an amount of 0.1 to 5 percent.
  • a process according to claim 5 wherein the noble metal is a platinum-rhodium alloy containing 1 to 49 percent rhodium.
  • the noble metal is a platinum-palladium alloy containing 1 to 49 percent palladium.
  • a process according to claim 12 wherein the noble metal is a platinum-rhodium alloy containing 1 to 49 percent rhodium.
  • a process of preparing the product of claim 1 wherein the oxygen containing atmosphere is air.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
US792110*A 1968-01-20 1969-01-17 Process of preparing noble metal materials having improved high temperature strength properties Expired - Lifetime US3622310A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19681608255 DE1608255A1 (de) 1968-01-20 1968-01-20 Durch innere Oxydation dispersionsgehaertete Werkstoffe auf Platin und Platin-Rhodium-Basis und Verfahren zu ihrer Herstellung

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CH (1) CH540984A (de)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4014692A (en) * 1976-01-09 1977-03-29 Owens-Corning Fiberglas Corporation Platinum-rhodium alloys having low creep rates
US4018599A (en) * 1975-09-05 1977-04-19 Engelhard Minerals & Chemicals Corporation Electrical contacts of dispersion strengthened gold
US4123263A (en) * 1977-11-02 1978-10-31 Owens-Corning Fiberglas Corporation Platinum-rhodium alloys
US4274852A (en) * 1979-08-17 1981-06-23 Owens-Corning Fiberglas Corporation Manufacturing glass with a bushing having a directionally aligned dispersion strengthened tip plate
US4374668A (en) * 1981-04-29 1983-02-22 The United States Of America As Represented By The Secretary Of The Navy Gold based electrical materials
US5518691A (en) * 1993-07-29 1996-05-21 Tanaka Kikinzoku Kogyo K.K. Precious metal material
US5730931A (en) * 1995-08-25 1998-03-24 Degussa Aktiengesellschaft Heat-resistant platinum material
US6242104B1 (en) * 1995-10-27 2001-06-05 Implico B.V. Precious metal composition and artifacts made therefrom
US20020136660A1 (en) * 2000-06-28 2002-09-26 Toru Shoji Method for producing platinum material reinforced with dospersed oxide
US6511523B2 (en) * 2000-06-28 2003-01-28 Tanaka Kikinzoku Kogyo K.K. Platinum material reinforced by oxide-dispersion and process for producing the same
US6572670B1 (en) * 2000-11-14 2003-06-03 Board Of Trustees Of University Of Illinois Colored metal clay and colored metals
US20030124015A1 (en) * 2001-04-13 2003-07-03 Haruki Yamasaki Method for preparing reinforced platinum material
WO2002098275A3 (en) * 2001-06-05 2004-01-29 Applied Med Resources Surgicals metals with improved hardness and methods of making same
US20040099345A1 (en) * 2002-01-30 2004-05-27 Erhard Dick Component which is intended for a facility for producing or preparing glass melts
US20050104712A1 (en) * 2003-11-13 2005-05-19 Habboosh Samir W. Extended temperature range thermal variable-resistance device
US20050133122A1 (en) * 2003-12-23 2005-06-23 General Electric Company High temperature alloys, and articles made and repaired therewith
US6982059B2 (en) * 2001-10-01 2006-01-03 General Electric Company Rhodium, platinum, palladium alloy
US20060139142A1 (en) * 2003-11-13 2006-06-29 Harco Laboratories, Inc. Extended temperature range heater
US20060202792A1 (en) * 2003-11-13 2006-09-14 Habboosh Samir W Thermal variable resistance device with protective sheath
US20090230391A1 (en) * 2008-03-11 2009-09-17 Fujitsu Limited Resistance Storage Element and Method for Manufacturing the Same
US20100276646A1 (en) * 2007-02-14 2010-11-04 W.C. Heraeus Gmbh Pt or pt alloy materials hardened by oxide dispersion, produced by inner oxidation and having proportions of oxide and good ductility
US20170137312A1 (en) * 2014-04-11 2017-05-18 Furuya Metal Co., Ltd. Stirrer for glass melting, and glass melting furnace
DE19922928B4 (de) * 1998-05-20 2018-02-22 Denso Corporation Temperaturfühler einer Thermistorbauart
CN111519058A (zh) * 2020-04-29 2020-08-11 重庆国际复合材料股份有限公司 一种原位合成纳米氧化物颗粒弥散强化铂基合金材料的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2406172A (en) * 1942-02-07 1946-08-20 Baker And Co Inc Platinum or allied metals, or their alloys, and articles made therefrom
US2636819A (en) * 1951-01-31 1953-04-28 Baker & Co Inc Grain stabilizing metals and alloys
US3515542A (en) * 1967-01-27 1970-06-02 Mallory & Co Inc P R Method of making dispersion-strengthened ductile materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2406172A (en) * 1942-02-07 1946-08-20 Baker And Co Inc Platinum or allied metals, or their alloys, and articles made therefrom
US2636819A (en) * 1951-01-31 1953-04-28 Baker & Co Inc Grain stabilizing metals and alloys
US3515542A (en) * 1967-01-27 1970-06-02 Mallory & Co Inc P R Method of making dispersion-strengthened ductile materials

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4018599A (en) * 1975-09-05 1977-04-19 Engelhard Minerals & Chemicals Corporation Electrical contacts of dispersion strengthened gold
US4014692A (en) * 1976-01-09 1977-03-29 Owens-Corning Fiberglas Corporation Platinum-rhodium alloys having low creep rates
US4123263A (en) * 1977-11-02 1978-10-31 Owens-Corning Fiberglas Corporation Platinum-rhodium alloys
US4274852A (en) * 1979-08-17 1981-06-23 Owens-Corning Fiberglas Corporation Manufacturing glass with a bushing having a directionally aligned dispersion strengthened tip plate
US4374668A (en) * 1981-04-29 1983-02-22 The United States Of America As Represented By The Secretary Of The Navy Gold based electrical materials
US5518691A (en) * 1993-07-29 1996-05-21 Tanaka Kikinzoku Kogyo K.K. Precious metal material
US5730931A (en) * 1995-08-25 1998-03-24 Degussa Aktiengesellschaft Heat-resistant platinum material
US6242104B1 (en) * 1995-10-27 2001-06-05 Implico B.V. Precious metal composition and artifacts made therefrom
DE19922928B4 (de) * 1998-05-20 2018-02-22 Denso Corporation Temperaturfühler einer Thermistorbauart
US20020136660A1 (en) * 2000-06-28 2002-09-26 Toru Shoji Method for producing platinum material reinforced with dospersed oxide
US6511523B2 (en) * 2000-06-28 2003-01-28 Tanaka Kikinzoku Kogyo K.K. Platinum material reinforced by oxide-dispersion and process for producing the same
US6841121B2 (en) * 2000-06-28 2005-01-11 Tanaka Kikinzoku Kogyo K.K. Process for producing oxide-dispersion strengthened platinum material
US6572670B1 (en) * 2000-11-14 2003-06-03 Board Of Trustees Of University Of Illinois Colored metal clay and colored metals
US20030205107A1 (en) * 2000-11-14 2003-11-06 Board Of Trustees Of University Of Illinois Colored metal clay and colored metals
US20030124015A1 (en) * 2001-04-13 2003-07-03 Haruki Yamasaki Method for preparing reinforced platinum material
US7217388B2 (en) * 2001-04-13 2007-05-15 Tanaka Kikinzoku Kogyo K.K. Method for preparing reinforced platinum material
WO2002098275A3 (en) * 2001-06-05 2004-01-29 Applied Med Resources Surgicals metals with improved hardness and methods of making same
US6982059B2 (en) * 2001-10-01 2006-01-03 General Electric Company Rhodium, platinum, palladium alloy
US20040099345A1 (en) * 2002-01-30 2004-05-27 Erhard Dick Component which is intended for a facility for producing or preparing glass melts
US7782171B2 (en) 2003-11-13 2010-08-24 Harco Laboratories, Inc. Extended temperature range heater
US7026908B2 (en) * 2003-11-13 2006-04-11 Harco Laboratories, Inc. Extended temperature range thermal variable-resistance device
US20060139142A1 (en) * 2003-11-13 2006-06-29 Harco Laboratories, Inc. Extended temperature range heater
US20060202792A1 (en) * 2003-11-13 2006-09-14 Habboosh Samir W Thermal variable resistance device with protective sheath
US20050104712A1 (en) * 2003-11-13 2005-05-19 Habboosh Samir W. Extended temperature range thermal variable-resistance device
US7915994B2 (en) 2003-11-13 2011-03-29 Harco Laboratories, Inc. Thermal variable resistance device with protective sheath
US7722729B2 (en) 2003-12-23 2010-05-25 General Electric Company Method for repairing high temperature articles
US20050133122A1 (en) * 2003-12-23 2005-06-23 General Electric Company High temperature alloys, and articles made and repaired therewith
US20090053424A1 (en) * 2003-12-23 2009-02-26 General Electric Company Method for repairing high temperature articles
US7494619B2 (en) 2003-12-23 2009-02-24 General Electric Company High temperature alloys, and articles made and repaired therewith
US20100276646A1 (en) * 2007-02-14 2010-11-04 W.C. Heraeus Gmbh Pt or pt alloy materials hardened by oxide dispersion, produced by inner oxidation and having proportions of oxide and good ductility
US8226855B2 (en) * 2007-02-14 2012-07-24 Heraeus Materials Technology Gmbh & Co. Kg Pt or Pt alloy materials hardened by oxide dispersion, produced by inner oxidation and having proportions of oxide and good ductility
US20090230391A1 (en) * 2008-03-11 2009-09-17 Fujitsu Limited Resistance Storage Element and Method for Manufacturing the Same
US20170137312A1 (en) * 2014-04-11 2017-05-18 Furuya Metal Co., Ltd. Stirrer for glass melting, and glass melting furnace
US10858276B2 (en) * 2014-04-11 2020-12-08 Furuya Metal Co., Ltd. Stirrer for glass melting, and glass melting furnace
CN111519058A (zh) * 2020-04-29 2020-08-11 重庆国际复合材料股份有限公司 一种原位合成纳米氧化物颗粒弥散强化铂基合金材料的制备方法
CN111519058B (zh) * 2020-04-29 2021-10-15 重庆国际复合材料股份有限公司 一种原位合成纳米氧化物颗粒弥散强化铂基合金材料的制备方法

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CH540984A (de) 1973-10-15

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