US20250305094A1 - High-hardness precious metal alloy and method for producing the same - Google Patents

High-hardness precious metal alloy and method for producing the same

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Publication number
US20250305094A1
US20250305094A1 US18/700,703 US202218700703A US2025305094A1 US 20250305094 A1 US20250305094 A1 US 20250305094A1 US 202218700703 A US202218700703 A US 202218700703A US 2025305094 A1 US2025305094 A1 US 2025305094A1
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United States
Prior art keywords
atom
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precious metal
metal alloy
temperature
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Pending
Application number
US18/700,703
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English (en)
Inventor
Masato Ebisugi
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Tanaka Precious Metal Technologies Co Ltd
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Tanaka Precious Metal Technologies Co Ltd
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Assigned to TANAKA KIKINZOKU KOGYO, K.K. reassignment TANAKA KIKINZOKU KOGYO, K.K. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: EBISUGI, Masato
Assigned to TANAKA PRECIOUS METAL TECHNOLOGIES CO., LTD. reassignment TANAKA PRECIOUS METAL TECHNOLOGIES CO., LTD. CHANGE OF NAME Assignors: TANAKA KIKINZOKU KOGYO K. K.
Publication of US20250305094A1 publication Critical patent/US20250305094A1/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • C22C5/02—Alloys based on gold
    • 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
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • 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
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • 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

  • a texture formed by spinodal decomposition is referred to as so-called modulated texture.
  • the modulated texture is periodically varied in concentration, and circumferentially forms an internal stress field and thus contributes to an increase in hardness.
  • the resistance force (critical shear stress) of dislocation motion in such a periodic internal stress field is expressed by the following expression, and the lattice strain (e), the elastic coefficient (Y), and the modulation amplitude in concentration (A) are considered to be control factors (examples of specific reference documents include Masaharu KATO, Introduction to the Theory of Dislocations (issued on August, 1999, publication: Shokado)).
  • An ordered phase generated by ordering contributes to an increase in hardness of the alloy due to each factor: (i) the Burgers vector of dislocation increases, (ii) an antiphase boundary can occur in the ordered phase, and (iii) the change in volume due to ordering results in distortion of the lattices in the interior of the ordered phase and the exterior of the ordered phase and acts on suppression of dislocation motion.
  • the precious metal alloy of the present invention includes both metals constituting a Pt—Ni-based alloy known as a combination of metals which generate ordering.
  • the ordering in the Pt—Ni-based alloy is expressed by a solution treatment and an aging treatment, and is known to be achieved by an aging treatment in an order-disorder transformation region or air cooling or the like started from a single phase region to result in hardening.
  • the ordering in the Pt—Ni-based alloy can provide hardening with an ordered phase of an L1 0 -type structure or an L1 2 -type structure.
  • the precious metal alloy of the present invention can achieve increased hardness with an ordered phase generated by ordering as in the above Pt—Ni-based alloy.
  • the configuration of the ordered phase in the present invention is not necessarily completely clear, the configuration is considered to correspond to a phase having a crystal structure which is the same as or similar to the ordered phase generated in the above Pt—Ni-based alloy.
  • such a phase is a phase including at least Pt and Ni and having a fcc structure and/or a fct structure.
  • the ordered phase in the present invention is presumed to be preferably a phase of an L1 0 -type structure or an L1 2 -type structure, or a crystal structure similar thereto.
  • the precious metal alloy of the present invention is a Pt—Au—Ni—Pd quaternary alloy.
  • Pt—Au—Ni—Pd quaternary alloy With respect to a binary phase diagram constituted with metal elements among Au, Ni, Pd, and Pt, Au—Ni-based, Au—Pt-based, and Pt—Pd-based alloys are two-phase separation type alloys. It can be seen from Table 2 above that there are many combinations of elements, in which the mixing enthalpy between metal elements among Au, Ni, Pd, and Pt is positive. It is thus considered that the Pt—Au—Ni—Pd-based alloy is highly liable to have a high mixing enthalpy and exhibit phase separation in a low temperature region.
  • the Pt—Au—Ni—Pd quaternary alloy highly possibly expresses spinodal decomposition and the concentration amplitude (A) due to such expression is also large.
  • Pt and Ni are relatively high in Young's modulus and thus are considered to be also high in elastic coefficient (Y).
  • Ni is large in difference in lattice constant from those of Au, Pt, and Pd and thus is considered to be also high in lattice strain (s).
  • the constituent metals of the precious metal alloy of the present invention are considered to correspond to a suitable combination for achieving expression of spinodal decomposition and an increase in hardness due to spinodal decomposition.
  • the action of each metal constituting the present invention is described.
  • Pt is an essential element for spinodal decomposition in the alloy system of the present invention.
  • Spinodal decomposition is not expressed at a too high or too low Pt concentration, and the concentration range of Pt, necessary for expression, is present.
  • Pt can be taken with Ni to form an ordered phase, contributing to an increase in hardness.
  • the Young's modulus of Pt is as relatively high as 169.9 GPa.
  • Pt can be expected as a metal which allows for an increase in amount of hardening of the alloy in expression of spinodal decomposition.
  • Au is also an essential element for expression of spinodal decomposition in the alloy system of the present invention.
  • Spinodal decomposition is not expressed at a too high or too low Au concentration, and the concentration range of Au, necessary for expression, is present. If the Au concentration is out of an optimal range, usual nucleation/growth easily occurs and no suitable increase in hardness can be obtained.
  • Such quenching in a high temperature region in the cooling treatment has the same meaning as quenching in the above solution treatment, and the cooling rate is preferably 10° C./s or more, more preferably 50° C./s or more.
  • the cooling rate in a temperature region of less than 600° C. is 2.5° C./s or less, preferably 1° C./s or less. It is preferable to perform cooling to room temperature with isothermal holding or adjustment of the cooling rate in a temperature region of less than 600° C.
  • the residence time in a temperature region of less than 600° C. is thus increased, thereby allowing for progression of spinodal decomposition and/or ordering and production of the precious metal alloy of the present invention.
  • the method for producing the precious metal alloy, including the cooling treatment, although has a difficulty in monitoring the cooling rate, has an effect comparable with that of the above production method with the solution treatment and the aging treatment which are combined.
  • the production method can allow the aging treatment step to be omitted.
  • the production method also has the advantages of allowing for suppression or decrease of quench crack, the change in dimension, and deformation which can occur in the case of excess quenching performed in the solution treatment.
  • the test piece after the solution treatment was heated and held at 300 to 650° C. for 1 hour. Thereafter, such a specimen piece after the aging treatment was embedded in a resin for the purpose of removal of an oxidized layer and residual stress due to thermal strain, and subjected to rough polishing (#500, #800, #1200) and mirror polishing in diamond suspensions of 1 ⁇ m and 1 ⁇ 4 ⁇ m. As described above, samples of various compositions were produced.
  • FIG. 5 respectively illustrate the results of XRD of the precious metal alloys of Example 20 (Pt67.5-Au10-Ni17.5-Pd5), Example 36 (Pt35-Au10-Ni35-Pd20), Example 71 (Pt42.5-Au10-Ni42.5-Pd5), and Example 75 (Pt37.5-Au10-Ni37.5-Pd15).
  • FIG. 6 and FIG. 7 respectively illustrate the results of XRD of the precious metal alloys of Comparative Example 13 (Pt22.5-Au10-Ni22.5-Pd45) and Comparative Example 11 (Pt30-Au10-Ni30-Pd30).
  • the drawings each illustrates an XRD diffraction profile for confirmation of spinodal decomposition in (a) and an XRD diffraction profile for confirmation of an ordered phase in (b).
  • FIG. 5 illustrates the results of XRD of the precious metal alloy (Pt22.5-Au10-Ni22.5-Pd45) of Comparative Example 13.
  • a side band peak was not observed at both sides of a diffraction peak and a side band peak was not observed also at one side in an XRD profile of the aging material of the precious metal alloy of Comparative Example 13.

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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)
  • Adornments (AREA)
  • Contacts (AREA)
  • Dental Preparations (AREA)
US18/700,703 2021-10-15 2022-10-04 High-hardness precious metal alloy and method for producing the same Pending US20250305094A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2021-169887 2021-10-15
JP2021169887 2021-10-15
PCT/JP2022/037042 WO2023063156A1 (ja) 2021-10-15 2022-10-04 高硬度貴金属合金及びその製造方法

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US20250305094A1 true US20250305094A1 (en) 2025-10-02

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US (1) US20250305094A1 (https=)
EP (1) EP4379078A4 (https=)
JP (1) JPWO2023063156A1 (https=)
KR (1) KR20240073963A (https=)
CN (1) CN118019867A (https=)
TW (1) TWI844981B (https=)
WO (1) WO2023063156A1 (https=)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024214666A1 (ja) * 2023-04-14 2024-10-17 田中貴金属工業株式会社 高硬度Ａｕ－Ｎｉ－Ｐｄ－Ｐｔ系貴金属合金
TWI898709B (zh) * 2023-07-11 2025-09-21 日商田中貴金屬工業股份有限公司 高硬度Ａｕ－Ｎｉ－Ｐｄ－Ｐｔ系貴金屬合金
CN117448620B (zh) * 2023-10-30 2026-03-13 中国科学院物理研究所 热电合金薄膜材料及其制备方法和用途

Family Cites Families (11)

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JPS56156729A (en) * 1980-05-02 1981-12-03 Ishifuku Kinzoku Kogyo Kk Platinum alloy for decoration
JPH0419862Y2 (https=) 1986-10-31 1992-05-07
JPH04147932A (ja) * 1990-10-08 1992-05-21 Citizen Watch Co Ltd 腕時計外装用Ｐｔ合金
JP2004093355A (ja) * 2002-08-30 2004-03-25 Toshiba Corp Ｐｄ合金系プローブピンおよびそれを用いたプローブピン装置
JP4216823B2 (ja) 2005-03-04 2009-01-28 田中貴金属工業株式会社 プローブピン及び該ブロ−ブビンを備えたブロ−ブカ−ド
US7959855B2 (en) * 2006-10-19 2011-06-14 Heru Budihartono White precious metal alloy
JP4878401B1 (ja) 2011-05-17 2012-02-15 石福金属興業株式会社 プローブピン用材料、プローブピン及びその製造方法
JP6372952B2 (ja) 2013-10-25 2018-08-15 石福金属興業株式会社 Ｐｔ基合金で構成されるプローブピン用材料、プローブピンの製造方法
US10858722B2 (en) * 2018-09-21 2020-12-08 Deringer-Ney, Inc. Platinum-nickel-based alloys, products, and methods of making and using same
US11939653B2 (en) * 2018-11-30 2024-03-26 Tanaka Kikinzoku Kogyo K.K. Electrically-conductive material having excellent wear resistance and heat resistance
CN111139372B (zh) * 2020-01-15 2020-12-11 贵研铂业股份有限公司 一种含有贵稀有金属的钯合金及其制备方法和用途

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Publication number Publication date
EP4379078A1 (en) 2024-06-05
KR20240073963A (ko) 2024-05-27
WO2023063156A1 (ja) 2023-04-20
EP4379078A4 (en) 2025-04-30
TWI844981B (zh) 2024-06-11
TW202330949A (zh) 2023-08-01
JPWO2023063156A1 (https=) 2023-04-20
CN118019867A (zh) 2024-05-10

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