EP3482850B1 - 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 - Google Patents

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 Download PDF

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Publication number
EP3482850B1
EP3482850B1 EP17200647.0A EP17200647A EP3482850B1 EP 3482850 B1 EP3482850 B1 EP 3482850B1 EP 17200647 A EP17200647 A EP 17200647A EP 3482850 B1 EP3482850 B1 EP 3482850B1
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EP
European Patent Office
Prior art keywords
weight
metallic phase
phase
article
moulding composition
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.)
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EP17200647.0A
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English (en)
French (fr)
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EP3482850A1 (de
Inventor
Bernard Bertheville
Yann Fallet
Jakob Kübarsepp
Märt Kolnes
Lauri Kollo
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Swatch Group Research and Development SA
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Swatch Group Research and Development SA
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Publication date
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Priority to EP17200647.0A priority Critical patent/EP3482850B1/de
Priority to US16/140,868 priority patent/US11015236B2/en
Priority to JP2018199750A priority patent/JP6764914B2/ja
Priority to CN201811324644.0A priority patent/CN109750206B/zh
Publication of EP3482850A1 publication Critical patent/EP3482850A1/de
Application granted granted Critical
Publication of EP3482850B1 publication Critical patent/EP3482850B1/de
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44F—SPECIAL DESIGNS OR PICTURES
    • B44F9/00—Designs imitating natural patterns
    • B44F9/10—Designs imitating natural patterns of metallic or oxidised metallic surfaces
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B29/00—Frameworks
    • G04B29/02—Plates; Bridges; Cocks
    • G04B29/027—Materials and manufacturing
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B37/00—Cases
    • G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects
    • G04B45/0076—Decoration of the case and of parts thereof, e.g. as a method of manufacture thereof
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/35—Iron
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/10—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
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • 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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
    • 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
    • C22C29/04—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 carbonitrides
    • 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
    • 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
    • C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0242—Making ferrous alloys by powder metallurgy using the impregnating technique
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0292—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with more than 5% preformed carbides, nitrides or borides

Definitions

  • the invention relates to a powder metallurgical molding composition intended for the manufacture of articles of sintered solid cermet, in particular of decorative or covering articles, comprising an inorganic powder intended to form the cermet and an organic binder.
  • the present invention also relates to a decorative or covering article and a clockwork mechanism element in sintered solid cermet made from such a molding composition as well as to a process for manufacturing an article by powder metallurgy. in solid sintered cermet.
  • Ceramic-metal composite materials In the manufacture of hard materials for making watch or jewelry parts, or even decorations for portable electronic devices (tablets, telephones, etc.), ceramic-metal composite materials, called cermets, are used. Such composite materials include a ceramic phase and a metallic phase or metallic binder. Solid cermets are obtained by powder metallurgy according to pressing or injection processes, followed by sintering, from a molding composition comprising an organic binder and an inorganic powder.
  • a cermet-type material For applications in watchmaking, jewelry and other portable electronic devices, and especially for decorative elements in contact with human skin, a cermet-type material must absolutely guarantee the absence of the release of allergenic elements.
  • the alternative metal binders proposed to date by manufacturers active in the field of cermets based on TiC, TiCN or TiN are mainly iron (Fe), iron-chromium (Fe-Cr) and iron- chromium-molybdenum (Fe-Cr-Mo), stainless steels and refractory steels.
  • cermet with a steel matrix comprising by weight up to 20% chromium, 1 to 5% boron, 2 to 8% silicon, 1.5 to 5% carbon, up to 5% % molybdenum, the remainder being iron.
  • a cermet with a metal binder based on an austenitic iron alloy which contains by weight less than 0.5% of carbon, from 2 to 26% of manganese, from 11 to 24% of chromium, from 2.5 to 10% molybdenum, less than 8% tungsten and 0.55 to 1.2% nitrogen.
  • all these cermets have resistance to corrosion in immersion in a saline environment as well as under salt spray which is extremely low, in particular after having undergone endings machining steps (mechanical, laser ) and / or polishings.
  • these cermets are advantageous for their high hardness, but their low resistance to corrosion is detrimental in the event of the presence of condensation inside the watch mechanism or for trim parts in contact with the watch. sweat of the wearer.
  • the object of the present invention is to remedy these drawbacks by proposing a composition for molding by powder metallurgy making it possible to manufacture articles, in particular decorative articles or cover, in sintered solid cermet not comprising allergenic elements such as nickel and / or cobalt, traditionally used.
  • Another object of the present invention is to provide a powder metallurgy molding composition making it possible to manufacture articles, in particular decorative or covering articles and elements of watch mechanisms, in solid sintered cermet highly resistant to corrosion by immersion in a saline environment and under saline mist.
  • Another object of the present invention is to provide a powder metallurgy molding composition furthermore exhibiting the same properties of hardness, toughness, density, luster, and tints, as the cermets available on the market for powder coating. manufacture of decorative or decorative articles in the fields of watchmaking, jewelry, or portable electronic devices.
  • the invention relates first of all to a powder metallurgy molding composition intended for the manufacture of articles in sintered solid cermet, comprising an inorganic powder intended to form the cermet and an organic binder.
  • said inorganic powder consists by weight of 35% to 95% of at least one ceramic phase based on ceramic chosen from the group consisting of TiC, TiCN, TiN and their mixtures, and from 5% to 65 % of a metallic phase, said metallic phase being constituted by weight of at least 40% iron, 15% to 45% chromium, 0.1% to 25% molybdenum, 0.1% to 10% silicon, from 0 to 10% of boron, and from 0 to 10% of niobium, the respective amounts of the elements of the metallic phase being such that their sum is equal to 100% by weight of the metallic phase.
  • Such a molding composition makes it possible to obtain articles in sintered solid cermet without an allergenic element such as nickel and / or cobalt, and highly resistant to salt corrosion.
  • Said article may, for example, be an article of decoration or cover or an element of a watch mechanism.
  • the present invention also relates to a process for the manufacture by powder metallurgy of a sintered solid cermet article comprising a step of preparing a molding composition as defined above, a molding step of said molding composition to produce a green part of the article, followed by debinding and sintering steps to obtain said sintered solid cermet article.
  • the present invention also relates to an article of decoration or covering in sintered solid cermet, in which said cermet is obtained from an inorganic powder consisting by weight of 35% to 95% of at least one ceramic phase based on ceramic selected from the group consisting of TiC, TiCN, TiN and mixtures thereof, and from 5% to 65% of a metallic phase, said metallic phase consisting by weight of at least 40% of iron, from 15% to 45 % chromium, from 0.1% to 25% of molybdenum, from 0.1% to 10% of silicon, from 0 to 10% of boron, and from 0 to 10% of niobium, the respective quantities of the elements of the metallic phase being such that their sum is equal to 100% by weight of the metallic phase.
  • the present invention also relates to a sintered solid cermet watch mechanism element, in which said cermet is obtained from an inorganic powder consisting by weight of 35% to 95% of at least one ceramic phase based on ceramic. chosen from the group consisting of TiC, TiCN, TiN and mixtures thereof, and from 5% to 65% of a metallic phase, said metallic phase consisting by weight of at least 40% of iron, from 15% to 45% of chromium, from 0.1% to 25% of molybdenum, from 0.1% to 10% of silicon, from 0 to 10% of boron, and from 0 to 10% of niobium, the respective quantities of the elements of the metallic phase being such that their sum is equal to 100% by weight of the metallic phase.
  • the powder metallurgy molding composition according to the invention comprises an inorganic powder intended to form a cermet and an organic binder.
  • the organic binder used in the molding composition according to the invention comprises in a known manner a polymeric structuring base of polyethylene and / or polypropylene type and / or copolymers, waxes of paraffin type which can be dissolved hot in organic solvents and / or polyethylenes glycol which can be dissolved in hot water and at least one organic surfactant of the stearic acid or stearate type.
  • Formulations of organic binders that are more complex and give excellent results can also be used. Such formulations are for example described in the international application WO 2014/191304 .
  • a mixer or a twin-screw extruder will preferably be used. More specifically, a heated mixer with high speed rotary knives, as described in the application EP 2801560 allows obtaining an intimate and homogeneous mixture of organic and inorganic powders.
  • the molding composition according to the invention comprises from 4% to 24% by weight of organic binder and 76% to 96% by weight of inorganic powders.
  • Said inorganic powder consists by weight of 35% to 95% of at least one ceramic phase and 5% to 65% of a metal phase, preferably 50% to 90% of the ceramic phase and 10% to 50% of the metallic phase, more preferably from 65% to 85% of the ceramic phase and from 15% to 35% of the metallic phase, and more preferably from 70% to 80% of the ceramic phase and from 20% to 30 % of the metallic phase.
  • the ceramic phase of the inorganic powder is based on a ceramic chosen from the group consisting of TiC, TiCN, TiN and their mixtures.
  • the ceramic phase is based on TiC or TiN.
  • the expression “ceramic phase based on an element” means that said ceramic phase contains at least 50% by weight of said element.
  • the ceramic phase of the inorganic powder consists by weight of 50% to 100% of a main ceramic phase based on ceramic chosen from the group consisting of TiC, TiCN, TiN, and mixtures thereof, and from 0 to 50% of at least one secondary ceramic phase chosen from the group comprising Cr 3 C 2 , CrN, NbC, NbN, TaC, TaN, and mixtures thereof.
  • the ceramic phase of the inorganic powder consists by weight of 80% to 100% of said main ceramic phase, and from 0 to 20% of said secondary ceramic phase, and more preferably from 90% to 100% of said phase main ceramic, and from 0 to 10% of said secondary ceramic phase.
  • said main ceramic phase of the inorganic powder may consist solely of TiC or may consist of TiN, the secondary ceramic phase being NbN (for example 90/10).
  • the metallic phase of the inorganic powder consists by weight of at least 40% iron, from 15% to 45% of chromium, from 0.1% to 25% of molybdenum, from 0.1% to 10% of silicon, from 0 to 10% of boron, and from 0 to 10% of niobium, the respective quantities of the elements of the metallic phase being such that their sum is equal to 100% by weight of the metallic phase.
  • the metallic phase of the inorganic powder consists predominantly of iron and chromium, and preferably comprises 40% to 70% by weight of iron, and more preferably 45% to 60% iron, and 20%. 40% chromium, and more preferably 25% to 35% chromium.
  • the metallic phase of the inorganic powder comprises by weight from 1% to 20% of molybdenum, and more preferably from 5% to 10% of molybdenum.
  • the metallic phase of the inorganic powder comprises by weight from 1% to 10% of silicon, and more preferably from 2% to 8% of silicon.
  • the metallic phase of the inorganic powder comprises by weight from 0% to 5% of boron, and more preferably from 0% to 1% of boron.
  • the metallic phase of the inorganic powder comprises by weight from 0% to 8% niobium, and more preferably from 0% to 5% niobium.
  • the metal phase according to the invention is therefore an alloy consisting of Fe, Cr, Mo, Si and optionally of B and / or Nb.
  • the metallic phase of the inorganic powder consists of at least 40% iron (preferably at least 45% iron), 25% to 35% chromium, 5% to 10% molybdenum, 2% to 8% silicon, 0% to 1% boron, and 0% to 5% niobium, the respective amounts of the elements of the metallic phase being such that their sum is equal to 100% by weight of the phase metallic.
  • the combination of Mo and Si in the Fe-Cr metallic phase makes it possible to obtain good resistance to corrosion in a saline environment.
  • the molding composition of the invention contains neither nickel nor cobalt.
  • the metallic phase is also free from manganese and carbon.
  • the present invention also relates to a process for the manufacture by powder metallurgy of a sintered solid cermet article comprising a step of preparing a molding composition as defined above, a molding step of said molding composition to produce a green part of the article, followed by debinding and sintering steps to obtain said sintered solid cermet article.
  • This molding step typically comprises a hot pressing or injection molding operation under pressure in a mold with cavities.
  • a hot pressing or injection molding operation under pressure in a mold with cavities.
  • the green part is cooled in the cavity and then is ejected from the mold.
  • the brown body is placed in a high temperature furnace (e.g. 1350 ° C - 1550 ° C) to obtain a dense sintered solid cermet article.
  • a high temperature furnace e.g. 1350 ° C - 1550 ° C
  • the method then comprises a step of finishing treatment of the appearance of the article, by machining (mechanical, laser, water jet, etc.) and / or by polishing.
  • the article may be an article of decoration or cover for watchmaking or jewelry or decorations of portable devices, or even an element of a clockwork mechanism.
  • the present invention also relates to a decorative or covering article made of sintered solid cermet, in particular a decorative or covering article obtained by the powder metallurgy manufacturing process using the molding composition described above.
  • the decorative or covering article according to the invention is made of sintered solid cermet, said sintered solid cermet having been obtained from an inorganic powder consisting by weight of 35% to 95% of at least one ceramic phase ceramic-based selected from the group consisting of TiC, TiCN, TiN and mixtures thereof, and from 5% to 65% of a metallic phase, said metallic phase consisting by weight of at least 40% of iron, 15 % to 45% of chromium, from 0.1% to 25% of molybdenum, from 0.1% to 10% of silicon, from 0 to 10% of boron, and from 0 to 10% of niobium, the respective quantities of the elements of the phase metallic being such that their sum is equal to 100% by weight of the metallic phase.
  • the present invention finally relates to an element of a sintered solid cermet watch mechanism, in particular an element of a watch mechanism obtained by the powder metallurgy manufacturing process using the molding composition described above.
  • the element of a watch mechanism according to the invention is made of sintered solid cermet, said sintered solid cermet having been obtained from an inorganic powder consisting by weight of 35% to 95% of at least one ceramic phase to ceramic base selected from the group consisting of TiC, TiCN, TiN and their mixtures, and from 5% to 65% of a metallic phase, said metallic phase consisting by weight of at least 40% iron, 15% to 45% chromium, 0.1% to 25% molybdenum, 0.1% to 10% silicon, 0 to 10% boron, and 0 to 10% niobium, the respective amounts of the elements of the metallic phase being such that their sum is equal to 100% by weight of the metallic phase .
  • the final composition of the sintered solid cermet depends on the sintering parameters used (temperature, duration of the sintering stage, pressure in the sintering chamber), it is preferable here to characterize the decorative or covering article or the element. of a clockwork mechanism of the invention by the composition of the cermet before sintering.
  • the molding composition of the invention makes it possible to obtain, by powder metallurgy, articles in sintered solid cermet, in particular decorative or covering articles, free from the allergenic elements traditionally used in cermets, such as nickel or cobalt.
  • the molding composition of the invention makes it possible to obtain, by powder metallurgy, articles in sintered solid cermet, in particular decorative or covering articles or watch mechanism elements, highly resistant to corrosion in saline environment, even after having undergone a finishing treatment.
  • the decorative or covering articles or the elements of the watch mechanism in sintered solid cermet of the invention have a hardness of between 1000 and 1800 Vickers, and are therefore particularly resistant to scratches, in a manner similar to the cermets traditionally used. .
  • the various elements used to produce the decorative or covering articles of the invention make it possible to obtain solid sintered cermets of low densities, that is to say of densities of less than 10 g / cm 3 .
  • the decorative or covering articles of the invention therefore have a pleasant wearing comfort, in particular when they relate to horological articles and consist for example of caps, middle parts, watch cases or bracelets.
  • the decorative or covering articles in sintered solid cermet of the invention exhibit, after polishing, a beautiful metallic luster, like the cermets traditionally used.
  • the decorative or covering articles in solid sintered cermet of the invention have white to gray and gray-pink to pink tints for the cermets based on TiC and TiCN, and yellow to yellow-bronze tints for the cermets with TiN base.
  • the decorative or covering articles in sintered solid cermet of the invention are decorative or covering articles for watches or jewelry, as well as articles for covering or protecting portable electronic devices, such as cell phones and tablets.
  • the sintered solid cermet watch mechanism elements of the invention are in particular functional elements. These elements according to the invention have a high hardness and are resistant to corrosion in the event of the presence of condensation inside the clockwork mechanism.
  • Such an element can for example be a plate.
  • This element is traditionally made from solid brass in which holes are machined for driving rubies with a small diameter hole in their center for inserting axle pivots. This brass must then be protected from corrosion by a surface deposit of nickel.
  • a solid cermet plate according to the invention having a high hardness, and produced by pressure or injection molding processes in accordance with the manufacturing process of the invention, allows the direct insertion of the pins. axles, without driving in or using rubies and does not require the use of a surface treatment to protect it from corrosion.
  • Articles in sintered solid cermet are made from molding compositions comprising the various inorganic powders indicated in Table I below, and as organic binder a binder comprising a polyethylene as structuring organic, a paraffin wax dissolving hot in heptane, in ethanol or in isopropanol, and as a surfactant for stearic acid.
  • organic binder a binder comprising a polyethylene as structuring organic, a paraffin wax dissolving hot in heptane, in ethanol or in isopropanol, and as a surfactant for stearic acid.
  • the inorganic powders all comprise by weight 70% of a ceramic phase consisting of 100% TiC and 30% of a metallic phase comprising nominally by weight at least iron and 28% chromium before sintering.
  • An article according to the invention is produced in the same way in which the Fe-Cr metallic phase contains both molybdenum and silicon (example 10).
  • the sintered parts are then machined and polished mechanically or in bulk to obtain final parts.
  • the hardness is measured using a Wolpert durometer fitted with a Vickers point (pyramid with a square base) and under an applied load of 30 kg. Beforehand, a calibration is carried out on a referenced standard of hardness comparable to that of cermets.
  • the hardness should be between 1000 and 1800 Vickers.
  • the toughness value represents the ability of a material to resist the propagation of a crack following an impact.
  • the toughness measured by Vickers indentations must be at least 4.5 MPa.m 1/2 .
  • the porosity rate is estimated using image acquisition software making it possible to discriminate on a polished surface and at 100x magnification, the different contrast zones.
  • the measured porosity is therefore a surface porosity.
  • a low porosity rate is directly linked to good quality and a beautiful shine of the surface after polishing.
  • Corrosion resistance is measured using a certified salt spray chamber (ASCOTT S120XP) in which the sample is positioned at an incline and will then undergo a salt spray (5% NaCl) for 72 hours, at the temperature of 35 ° C.
  • ASCOTT S120XP certified salt spray chamber
  • Example 10 The results of Table I show that only the molding composition according to the invention (Example 10) comprising an Fe-Cr-Mo-Si metallic phase makes it possible to obtain an article in sintered solid cermet, without nickel or cobalt, exhibiting good corrosion resistance in saline environment.
  • the comparative examples (Examples 1 to 9) without Mo or without Si show only low resistance to corrosion in a saline environment.
  • Articles according to the invention are produced according to the process of Examples 1 to 10.
  • the inorganic powders all comprise by weight 70% of a ceramic phase consisting of 100% TiC and 30% of a metallic phase consisting nominally by weight of iron, 28% chromium, 8% molybdenum, 4% silicon and 0.2% to 0.6% boron before sintering.
  • Table II Table II Ex. Composition of the inorganic powder before sintering Hardness (HV 30 ) Tenacity (MPa.m 1/2 ) Porosity rate (%) Corrosion resistance 11 70TiC-FeCr28Mo8Si4B0.2 1441 7.2 1.58 Very good 12 70TiC-FeCr28Mo8Si4B0.4 1444 7.7 3.01 Very good 13 70TiC-FeCr28Mo8Si4B0.6 1422 7.9 1.55 Very good
  • Examples 11 to 13 of the invention show that the addition of a small quantity of boron makes it possible to increase the resistance to corrosion in a saline environment.
  • the addition of boron increases toughness.
  • the measured tenacity of 6.1 MPa.m 1/2 for example 10 of the invention, without boron goes to the maximum value of 7.9 MPa.m 1/2 for example 13 of the invention, comprising a nominal quantity by mass of 0.6% of boron.
  • the inorganic powder comprises by weight 75% of a ceramic phase consisting of 100% TiC and 25% of a metallic phase consisting nominally by weight of 49.6. % iron, 34% chromium, 8% molybdenum, 4% silicon, 4% niobium and 0.4% boron before sintering.
  • Table III Table III Ex. Composition of the inorganic powder before sintering Hardness (HV 30 ) Tenacity (MPa.m 1/2 ) Porosity rate (%) Corrosion resistance 14 75TiC-FeCr34Mo8Si4Nb4B0.4 1528 6.4 0.39 Very good
  • Example 14 of the invention shows that the addition of niobium also makes it possible to increase the resistance to corrosion in a saline environment.
  • the addition of niobium makes it possible to improve the homogeneity of the metal phase and thus to reduce the porosity and increase the hardness of the cermet obtained.
  • the inorganic powder comprises by weight 80% of a ceramic phase consisting nominally by weight of 90% of TiN (main ceramic phase) and of 10% of NbN. (secondary ceramic phase), and 20% of a metallic phase consisting nominally by weight of 59% iron, 28% chromium, 8% molybdenum, and 5% silicon, before sintering.
  • the hardness and the corrosion resistance are measured as for Examples 1 to 10.
  • Table IV Table IV Ex. Composition of the inorganic powder before sintering Hardness (HV 30 ) Corrosion resistance 15 TiN-10NbN-FeCr28Mo8Si5 1108 good
  • Example 15 of the invention comprising a main ceramic phase TiN and a secondary ceramic phase NbN, as well as a metallic phase Fe-Cr-Mo-Si exhibits good resistance to corrosion in a saline medium.

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Claims (14)

  1. Komposition zum pulvermetallurgischen Giessen, die zur Herstellung von Verzierungs- oder Ausstattungsartikeln oder eines Elements eines Mechanismus für die Uhrmacherei aus gesintertem massivem Cermet bestimmt ist, ein anorganisches Pulver, das dazu bestimmt ist, das Cermet zu bilden, und ein organisches Bindemittel umfassend, dadurch gekennzeichnet, dass das anorganische Pulver in Gewicht aus 35 % bis 95 % mindestens einer keramischen Phase auf Basis von Keramik gebildet ist, die aus der Gruppe ausgewählt ist, die aus TiC, TiCN, TiN und deren Gemischen gebildet ist, und aus 5 % bis 65 % einer metallischen Phase, wobei die metallische Phase in Gewicht aus mindestens 40 % Eisen, aus 15 % bis 45 % Chrom, aus 0,1 % bis 25 % Molybdän, aus 0,1 % bis 10 % Silicium, aus 0 bis 10 % Bor, und aus 0 bis 10 % Niob gebildet ist, wobei die jeweiligen Mengen der Elemente der metallischen Phase derart sind, dass ihre Summe gleich 100 Gew.-% der metallischen Phase ist.
  2. Komposition zum Giessen nach Anspruch 1, dadurch gekennzeichnet, dass die metallische Phase in Gewicht von 40 % bis 70 % Eisen, vorzugsweise von 45 % bis 60 % Eisen umfasst.
  3. Komposition zum Giessen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die metallische Phase in Gewicht von 20 % bis 40 % Chrom, und vorzugsweise von 25 % bis 35 % Chrom umfasst.
  4. Komposition zum Giessen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die metallische Phase in Gewicht von 1 % bis 20 % Molybdän, und vorzugsweise von 5 % bis 10 % Molybdän umfasst.
  5. Komposition zum Giessen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die metallische Phase in Gewicht von 1 % bis 10% Silicium, und vorzugsweise von 2% bis 8 % Silicium umfasst.
  6. Komposition zum Giessen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die metallische Phase in Gewicht von 0 % bis 5 % Bor, und vorzugsweise von 0 % bis 1 % Bor umfasst.
  7. Komposition zum Giessen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die metallische Phase in Gewicht 0 % bis 8 % Niob, und vorzugsweise von 0 % bis 5 % Niob umfasst.
  8. Komposition zum Giessen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass die keramische Phase in Gewicht aus 50 % bis 100 % einer keramischen Hauptphase auf Basis von Keramik gebildet ist, die aus der Gruppe ausgewählt ist, die aus TiC, TiCN, TiN und deren Gemischen gebildet ist, und aus 0 bis 50 % mindestens einer keramischen Sekundärphase, die aus der Gruppe ausgewählt ist, die Cr3C2, CrN, NbC, NbN, TaC, TaN und deren Gemische umfasst.
  9. Komposition zum Giessen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das anorganische Pulver in Gewicht aus 50 % bis 90 % der keramischen Phase und aus 10 % bis 50 % der metallischen Phase, und vorzugsweise aus 65 % bis 85 % der keramischen Phase und aus 15 % bis 35 % der metallischen Phase gebildet ist.
  10. Komposition zum Giessen nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass sie in Gewicht von 76 % bis 96 % eines anorganischen Pulvers und von 4 % bis 24 % eines organischen Bindemittels umfasst.
  11. Verfahren zur Herstellung durch Pulvermetallurgie eines Artikels aus gesintertem massivem Cermet, umfassend einen Schritt zur Vorbereitung einer Komposition zum Giessen nach einem der Ansprüche 1 bis 10, einen Schritt zum Giessen der Komposition zum Giessen zum Fertigen eines Rohteils des Artikels, danach Schritte zum Entbinden und Sintern, um den Artikel aus gesintertem massivem Cermet zu erhalten.
  12. Verfahren zur Herstellung durch Pulvermetallurgie eines Artikels aus gesintertem massivem Cermet nach Anspruch 11, dadurch gekennzeichnet, dass der Artikel ein Verzierungs- oder Ausstattungsartikel ist.
  13. Verfahren zur Herstellung durch Pulvermetallurgie eines Artikels aus gesintertem massivem Cermet nach Anspruch 11, dadurch gekennzeichnet, dass der Artikel ein Element eines Mechanismus für die Uhrmacherei ist.
  14. Verzierungs- oder Ausstattungsartikel oder Element eines Mechanismus für die Uhrmacherei aus gesintertem massivem Cermet, dadurch gekennzeichnet, dass das gesinterte massive Cermet aus einem anorganischen Pulver erhalten wird, das aus einem anorganischen Pulver erhalten wird, das in Gewicht aus 35 % bis 95 % mindestens einer keramischen Phase auf Basis von Keramik gebildet ist, die aus der Gruppe ausgewählt ist, die aus TiC, TiCN, TiN und deren Gemischen gebildet ist, und aus 5 % bis 65 % einer metallischen Phase, wobei die metallische Phase in Gewicht aus mindestens 40 % Eisen, aus 15 % bis 45 % Chrom, aus 0,1 % bis 25 % Molybdän, aus 0,1 % bis 10 % Silicium, aus 0 bis 10 % Bor, und aus 0 bis 10 % Niob gebildet ist, wobei die jeweiligen Mengen der Elemente der metallischen Phase derart sind, dass ihre Summe gleich 100 Gew.-% der metallischen Phase ist.
EP17200647.0A 2017-11-08 2017-11-08 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 Active EP3482850B1 (de)

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EP17200647.0A EP3482850B1 (de) 2017-11-08 2017-11-08 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
US16/140,868 US11015236B2 (en) 2017-11-08 2018-09-25 Powder metallurgy moulding composition notably intended for manufacturing decorative or covering articles in sintered massive cermet and said decorative or covering articles in sintered massive cermet
JP2018199750A JP6764914B2 (ja) 2017-11-08 2018-10-24 塊状焼結サーメット製の装飾的又は被覆物品を製造することを特に目的とした粉末冶金成型組成物及び塊状焼結サーメット製の装飾的又は被覆物品
CN201811324644.0A CN109750206B (zh) 2017-11-08 2018-11-08 用于制造烧结块状金属陶瓷形式的装饰或覆盖制品的粉末冶金模制组合物和所述制品

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JPS52150418A (en) * 1976-06-09 1977-12-14 Tokushiyu Muki Zairiyou Kenkiy Manufacture of heat resisting tenacious cermet
US4615734A (en) * 1984-03-12 1986-10-07 General Electric Company Solid particle erosion resistant coating utilizing titanium carbide, process for applying and article coated therewith
JPH0617531B2 (ja) * 1986-02-20 1994-03-09 日立金属株式会社 強靭性サ−メツト
JPH0483805A (ja) * 1990-07-25 1992-03-17 Sumitomo Electric Ind Ltd 複合硬質合金材
JPH0726173B2 (ja) * 1991-02-13 1995-03-22 東芝タンガロイ株式会社 高靭性サーメット及びその製造方法
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KR102148055B1 (ko) 2013-05-28 2020-08-26 코마도 쏘시에떼 아노님 사출 성형 조성물용 바인더
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CN109750206A (zh) 2019-05-14
JP2019085646A (ja) 2019-06-06
US11015236B2 (en) 2021-05-25

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