EP3943630A1 - Cermet-komponente für uhrenherstellung oder schmuck - Google Patents

Cermet-komponente für uhrenherstellung oder schmuck Download PDF

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Publication number
EP3943630A1
EP3943630A1 EP20187228.0A EP20187228A EP3943630A1 EP 3943630 A1 EP3943630 A1 EP 3943630A1 EP 20187228 A EP20187228 A EP 20187228A EP 3943630 A1 EP3943630 A1 EP 3943630A1
Authority
EP
European Patent Office
Prior art keywords
carbide
weight
percentage
phase
tic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20187228.0A
Other languages
English (en)
French (fr)
Inventor
Bernard Bertheville
Yann Fallet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Swatch Group Research and Development SA
Original Assignee
Swatch Group Research and Development SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Priority to EP20187228.0A priority Critical patent/EP3943630A1/de
Priority to CN202180060014.0A priority patent/CN116134170A/zh
Priority to US18/004,691 priority patent/US20230250517A1/en
Priority to JP2023502742A priority patent/JP7542716B2/ja
Priority to EP21733442.4A priority patent/EP4185726A2/de
Priority to PCT/EP2021/066498 priority patent/WO2022017697A2/fr
Publication of EP3943630A1 publication Critical patent/EP3943630A1/de
Priority to JP2024075148A priority patent/JP2024109638A/ja
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/065—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on SiC
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • A44C27/003—Metallic alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/10—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on titanium carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the present invention relates to a component in particular for a timepiece or piece of jewelry, produced in a material of the cermet type with a ceramic phase comprising carbides and with a metal binder comprising a precious metal.
  • trim components are made of gold or a gold alloy.
  • Gold has the advantage of possessing great ductility as well as great malleability, which allows easy shaping. It is also endowed with a very high and characteristic metallic luster.
  • the different gold alloys can take on various hues ranging from white to red.
  • gold and its alloys have the disadvantage of having a low hardness which is at most 300 HV.
  • various ceramic composites have been developed in order to increase the hardness of gold. The manufacturing process most often involves infiltrating a high-hardness matrix with gold and applying very high pressures. The disadvantage of this method is that the accessible shapes remain limited to simple geometries, obtaining complex shapes requiring the use of additional machining methods.
  • cermets use a non-precious metal as a binder. It is often allergenic elements such as nickel or cobalt as disclosed in the document US 4,589,917 , or iron-based alloys resulting in low corrosion resistance and high ferromagnetism.
  • the present invention proposes a component in particular for a timepiece or piece of jewelry made of a cermet material comprising a phase of carbides and a phase of a metallic binder chosen from silver, gold, platinum , palladium, ruthenium, osmium, rhodium and one of their alloys.
  • the metal binder phase is present in a weight percentage between 3 and 25% and the carbides phase is present in a weight percentage between 75 and 97%.
  • the cermet material thus developed has, after polishing, a metallic luster which can be comparable to that observed in stainless steels, particularly when the metallic binder is palladium.
  • These precious cermets have hardnesses between 700 and 1900 HV30 and they have sufficient tenacity for the production of trim parts.
  • they can be shaped by processes conventional powder metallurgy techniques such as pressing or injection to obtain "near-net shape" parts.
  • the low content of precious binder makes it possible to obtain a cermet that retains the reflective and colorimetric characteristics of the carbide used, which is particularly important for trim and decorative components.
  • precious binders such as platinum or palladium makes it possible to densify these carbide-based cermets from much lower temperatures than those of said carbides alone and without resorting to sintering at high temperatures and under pressure, either from 1250°C with palladium and 1400°C with platinum.
  • the powders of the mixture preferably have a d50 of less than 20 ⁇ m, more preferably less than 10 ⁇ m and even more preferably less than 5 ⁇ m.
  • a small particle size the homogeneity of the mixture is improved and excellent coverage of the metallic binder on each carbide grain is guaranteed.
  • the final density is increased while increasing the mechanical properties such as hardness and toughness. after sintering. Also, reducing the particle size results in a high metallic luster, i.e. a high luminance value L*
  • the present invention relates to a component, in particular for a timepiece or piece of jewelry, made of a cermet-type material comprising a majority phase of carbides and a minority phase of a metallic binder comprising a precious element such as silver, gold, platinum, palladium, ruthenium, osmium, rhodium or an alloy of one of these precious elements.
  • the metallic binder is chosen from silver, gold, platinum, palladium or an alloy of one of these precious elements.
  • the component according to the invention can form a decorative article such as a constituent element of watches, jewellery, bracelets, etc.
  • this component can be a covering part such as a middle part, a back, a bezel, a pusher, a bracelet link, a dial, a hand, a dial index, etc. It can also be a component of the movement such as a mass oscillating, a turntable, etc.
  • a caseband 1 made with the cermet-type material according to the invention is shown in figure 1 .
  • This mixture comprises by weight between 75 and 97%, advantageously between 78 and 97%, and more advantageously between 78 and 94%, of the carbide powder and between 3 and 25%, advantageously between 3 and 22%, and more advantageously between 6 and 22% of the metal powder.
  • the mixture may optionally comprise one or more additives in a percentage by weight for all the additives of less than or equal to 4%. In the presence of one or more additives, the latter are preferably present in a percentage for all the additives of between 1 and 3% by weight.
  • the mixture comprises the carbide powder in a percentage by weight of between 75 and 96%, the powder of the metal binder in a percentage by weight of between 3 and 24% and the additive or additives in a percentage by weight for all the additives comprised between 1 and 3%.
  • additives are intended to improve the densification during sintering.
  • it may be a metal di-silicide such as Si 2 Ti or Si 2 Zr.
  • the carbide powder comprises one or more carbides chosen from TiC, SiC, Mo 2 C, WC and NbC. More particularly, the carbide powder mainly comprises titanium carbide (TiC), tungsten carbide (WC) or carbon carbide. molybdenum (Mo 2 C).
  • TiC titanium carbide
  • WC tungsten carbide
  • Mo 2 C molybdenum carbide
  • the metal powder mainly comprises palladium, platinum, silver, gold, ruthenium, osmium, rhodium or an alloy of one of these elements. It can, except for impurities, consist entirely of platinum, palladium, ruthenium, osmium, rhodium or silver.
  • the gold is preferentially present in alloyed form with at least one element chosen from Cu, Ag, Pd, In. More preferentially, the gold alloy comprises gold alloyed with silver and copper (gold 3N yellow, 5N red gold) or palladium (white gold).
  • the metal powder can also comprise carbon in a percentage by weight of between 0.1 and 5% relative to the total weight of the mixture of powders. Indeed, during sintering, part of the Mo 2 C can be transformed into Mo with the consequence of a reduction in hardness.
  • the addition of carbon makes it possible to limit the formation of Mo and therefore to maintain the level of hardness.
  • the addition of carbon can be carried out in the carbide powder.
  • the carbide powder thus comprises carbon in a percentage by weight of between 0.1 and 5% relative to the total weight of the mixture of powders.
  • the blank thus obtained is cooled and polished. It can also be machined before polishing to obtain the desired component.
  • the component which can also be described as an article, resulting from the manufacturing process comprises the carbide phase and the metallic phase in percentages by weight close to those of the starting powders.
  • the carbide phase comprises the carbides as well as any elements derived from the basic carbide powder such as Mo for the example above.
  • the metallic phase it comprises the compounds of the starting metallic powder as well as a possible compound resulting from a decomposition or reaction of the metallic base powder.
  • the latter can be found in the phase of carbides and/or in the metallic phase.
  • the component has a CIELAB colorimetric space (compliant with CIE n°15, ISO 7724/1, DIN 5033 Part 7, ASTM E-1164) with a luminance component L*, representative of the way the material reflects light, between 60 and 90, preferably between 65 and 85 and, more preferably between 70 and 85.
  • the ceramic material has an HV30 hardness between 700 and 1900 depending on the types and percentages of the constituents. More specifically, it has an HV30 hardness of between 700 and 1300 when the carbide phase mainly comprises molybdenum carbide. An HV30 hardness of between 900 and 1600 when the carbide phase mainly comprises tungsten carbide and an HV30 hardness of between 700 and 1900 when the carbide phase mainly comprises titanium carbide.
  • the ceramic material has a toughness K i c of at least 2 MPa.m 1/2 with values possibly exceeding 20 MPa.m 1/2 .
  • Tables 1 to 3 below show various examples of cermets according to the invention.
  • HV 30 hardness measurements were taken on the surface of the samples and the toughness was determined on the basis of the hardness measurements as described above.
  • the cermets with a carbide phase mainly comprising TiC generally have a higher hardness than that of the cermets with a carbide phase mainly comprising Mo 2 C.
  • the hardnesses are thus between 750 and 1800 HV30 for the cermets comprising TiC compared with values in the 750-1200 HV30 range for cermets comprising mainly Mo 2 C.
  • Sample 4 comprising TiC and an Au alloy has a lower hardness (761 HV30) attributed to a lower sintering time compared to sample 3 comprising TiC and an Au alloy (1209 HV30). Sample 4 also has a lower tenacity compared to sample 3.
  • Cermets comprising Mo 2 C and Pd exhibit extremely high toughness values which are greater than 10 MPa.m 1/2 for Pd contents greater than or equal to 8% (tests 6, 20, 21). For certain compositions, there is no crack propagation during the HV30 hardness measurements, a toughness value could therefore not be measured.
  • Cermets comprising mainly Mo 2 C have high luminance indices L* regardless of the type of precious binder used (Pt, Pd, Ag, Au-Cu) with values of the order of 80 against values in the range 70-75 for cermets mainly comprising TiC.
  • the figure 2 represents an electron microscopy of a sample sintered from the mixture of powders comprising by weight 80% Mo 2 C, 15% Au and 5% Cu.
  • the carbide phase is formed of the dark gray zone composed of Mo 2 C and the medium gray zone rich in Mo. Part of the Mo 2 C is transformed into Mo during sintering, resulting in a decrease in the hardness.
  • the metallic AuCu phase is the white phase.
  • the picture 3 shows an electron microscopy of a sample sintered from the powder mixture comprising by weight 80% TiC, 2% SiC and 18% Pt. There is the phase of carbides formed from the black and gray areas with the black area rich in TiC and the gray zone comprising TiC and Pt. In white, there is the metallic phase.
  • the invention relates to the component made of a cermet material.
  • This component was designed for applications in particular in the field of watchmaking and jewelery such as for example trim elements or the movement of a timepiece.
  • the component according to the invention cannot be limited to watchmaking.
  • this component can be applied in the field of tableware, cutlery, leather goods, jewelry or jewelry.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Powder Metallurgy (AREA)
  • Materials For Medical Uses (AREA)
  • Adornments (AREA)
EP20187228.0A 2020-07-22 2020-07-22 Cermet-komponente für uhrenherstellung oder schmuck Withdrawn EP3943630A1 (de)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP20187228.0A EP3943630A1 (de) 2020-07-22 2020-07-22 Cermet-komponente für uhrenherstellung oder schmuck
CN202180060014.0A CN116134170A (zh) 2020-07-22 2021-06-17 金属陶瓷制成的用于钟表或首饰的组件
US18/004,691 US20230250517A1 (en) 2020-07-22 2021-06-17 Component for timepiece or piece of jewellery made of cermet
JP2023502742A JP7542716B2 (ja) 2020-07-22 2021-06-17 サーメット製の計時器または宝飾品用の構成要素
EP21733442.4A EP4185726A2 (de) 2020-07-22 2021-06-17 Komponente für uhr oder schmuckstück aus cermet
PCT/EP2021/066498 WO2022017697A2 (fr) 2020-07-22 2021-06-17 Composant pour piece d'horlogerie ou de bijouterie en cermet
JP2024075148A JP2024109638A (ja) 2020-07-22 2024-05-07 サーメット製の計時器または宝飾品用の構成要素

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20187228.0A EP3943630A1 (de) 2020-07-22 2020-07-22 Cermet-komponente für uhrenherstellung oder schmuck

Publications (1)

Publication Number Publication Date
EP3943630A1 true EP3943630A1 (de) 2022-01-26

Family

ID=71741713

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20187228.0A Withdrawn EP3943630A1 (de) 2020-07-22 2020-07-22 Cermet-komponente für uhrenherstellung oder schmuck
EP21733442.4A Pending EP4185726A2 (de) 2020-07-22 2021-06-17 Komponente für uhr oder schmuckstück aus cermet

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP21733442.4A Pending EP4185726A2 (de) 2020-07-22 2021-06-17 Komponente für uhr oder schmuckstück aus cermet

Country Status (5)

Country Link
US (1) US20230250517A1 (de)
EP (2) EP3943630A1 (de)
JP (2) JP7542716B2 (de)
CN (1) CN116134170A (de)
WO (1) WO2022017697A2 (de)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH512952A (fr) * 1969-03-10 1971-09-30 Production Tool Alloy Co Ltd Outil de coupe
JPS5913045A (ja) * 1982-07-14 1984-01-23 Seiko Epson Corp 時計用外装部品
JPS5916946A (ja) * 1982-07-20 1984-01-28 Seiko Epson Corp 時計用外装部品
JPS5916945A (ja) * 1982-07-20 1984-01-28 Seiko Epson Corp 時計用外装部品
JPS5950152A (ja) * 1982-09-13 1984-03-23 Seiko Epson Corp 時計用外装部品
EP0121769A1 (de) * 1983-03-15 1984-10-17 Stellram S.A. Sinterlegierung auf Karbidbasis sowie Körper aus dieser Legierung
JPS60194044A (ja) * 1984-03-13 1985-10-02 Seiko Epson Corp 装飾部材用焼結材料
US4589917A (en) 1983-07-28 1986-05-20 Kyocera Corporation Decorative golden sintered alloy
JPS62235440A (ja) * 1986-04-02 1987-10-15 Seiko Epson Corp 装飾部材用焼結材料
US5015290A (en) * 1988-01-22 1991-05-14 The Dow Chemical Company Ductile Ni3 Al alloys as bonding agents for ceramic materials in cutting tools
WO2004005561A2 (fr) 2002-07-04 2004-01-15 Propension Synthese d’un materiau composite metal-ceramique a durete renforcee

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2180826A (en) * 1939-05-20 1939-11-21 Mallory & Co Inc P R Electric contact
GB828877A (en) * 1957-10-04 1960-02-24 Engelhard Ind Inc Improvements in or relating to spinerettes
JPS5726136A (en) * 1980-07-24 1982-02-12 Chugai Electric Ind Co Ltd Sintered noble metallic alloy with wear resistance
US5603075A (en) * 1995-03-03 1997-02-11 Kennametal Inc. Corrosion resistant cermet wear parts
JP2002105577A (ja) * 2000-09-28 2002-04-10 Kyocera Corp 装飾部材およびその製造方法
US20060086441A1 (en) * 2004-10-27 2006-04-27 University Of Cincinnati Particle reinforced noble metal matrix composite and method of making same
EP3482850B1 (de) 2017-11-08 2021-02-24 The Swatch Group Research and Development Ltd Zusammensetzung zum formgiessen durch pulvermetallurgie, die insbesondere für die herstellung von dekor- oder verkleidungsartikeln aus gesintertem massivem cermet bestimmt ist, und diese dekor- oder verkleidungsartikel aus gesintertem massivem cermet
DE102018105489A1 (de) * 2018-03-09 2019-09-12 Hnp Mikrosysteme Gmbh Verbundwerkstoffe auf Basis von Wolframcarbid mit Edelmetallbindern sowie Verwendung und Verfahren zu deren Herstellung
EP4219781A1 (de) 2018-11-16 2023-08-02 The Swatch Group Research and Development Ltd Metallmatrixverbundmaterial und verfahren zur herstellung eines metallmatrixverbundmaterials
CN109778044A (zh) * 2019-01-29 2019-05-21 广汉鸿达硬质合金有限责任公司 一种装饰品彩色合金材料

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH512952A (fr) * 1969-03-10 1971-09-30 Production Tool Alloy Co Ltd Outil de coupe
JPS5913045A (ja) * 1982-07-14 1984-01-23 Seiko Epson Corp 時計用外装部品
JPS5916946A (ja) * 1982-07-20 1984-01-28 Seiko Epson Corp 時計用外装部品
JPS5916945A (ja) * 1982-07-20 1984-01-28 Seiko Epson Corp 時計用外装部品
JPS5950152A (ja) * 1982-09-13 1984-03-23 Seiko Epson Corp 時計用外装部品
EP0121769A1 (de) * 1983-03-15 1984-10-17 Stellram S.A. Sinterlegierung auf Karbidbasis sowie Körper aus dieser Legierung
US4589917A (en) 1983-07-28 1986-05-20 Kyocera Corporation Decorative golden sintered alloy
JPS60194044A (ja) * 1984-03-13 1985-10-02 Seiko Epson Corp 装飾部材用焼結材料
JPS62235440A (ja) * 1986-04-02 1987-10-15 Seiko Epson Corp 装飾部材用焼結材料
US5015290A (en) * 1988-01-22 1991-05-14 The Dow Chemical Company Ductile Ni3 Al alloys as bonding agents for ceramic materials in cutting tools
WO2004005561A2 (fr) 2002-07-04 2004-01-15 Propension Synthese d’un materiau composite metal-ceramique a durete renforcee

Also Published As

Publication number Publication date
JP7542716B2 (ja) 2024-08-30
US20230250517A1 (en) 2023-08-10
WO2022017697A2 (fr) 2022-01-27
JP2024109638A (ja) 2024-08-14
WO2022017697A3 (fr) 2022-03-24
CN116134170A (zh) 2023-05-16
EP4185726A2 (de) 2023-05-31
JP2023533821A (ja) 2023-08-04

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