EP3482850B1 - Moulding composition by powder metallurgy, especially for producing sintered solid cermet lining or decorative articles and said sintered solid cermet lining or decorative articles - Google Patents

Moulding composition by powder metallurgy, especially for producing sintered solid cermet lining or decorative articles and said sintered solid cermet lining or decorative articles 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
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Prior art keywords
weight
metallic phase
phase
article
moulding composition
Prior art date
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EP17200647.0A
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German (de)
French (fr)
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EP3482850A1 (en
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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Priority to EP17200647.0A priority Critical patent/EP3482850B1/en
Priority to US16/140,868 priority patent/US11015236B2/en
Priority to JP2018199750A priority patent/JP6764914B2/en
Priority to CN201811324644.0A priority patent/CN109750206B/en
Publication of EP3482850A1 publication Critical patent/EP3482850A1/en
Application granted granted Critical
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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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Description

Domaine de l'inventionField of the invention

L'invention concerne une composition de moulage par métallurgie des poudres destinée à la fabrication d'articles en cermet massif fritté, notamment des articles de décor ou d'habillage, comprenant une poudre inorganique destinée à former le cermet et un liant organique. La présente invention concerne également un article de décor ou d'habillage et un élément de mécanisme d'horlogerie en cermet massif fritté réalisé à partir d'une telle composition de moulage ainsi qu'un procédé de fabrication par métallurgie des poudres d'un article en cermet massif fritté.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.

Arrière-plan de l'inventionBackground of the invention

Dans la fabrication de matériaux durs pour réaliser des pièces horlogères ou de bijouterie, ou encore de décors pour des appareils portables électroniques (tablettes, téléphones,...), on utilise des matériaux composites céramique-métal, appelés cermets. De tels matériaux composites comprennent une phase céramique et une phase métallique ou liant métallique. Les cermets massifs sont obtenus par métallurgie des poudres selon des procédés de pressage ou d'injection, suivis d'un frittage, à partir d'une composition de moulage comprenant un liant organique et une poudre inorganique.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.

Plus spécifiquement, le procédé global de fabrication d'un article en cermet massif réalisé par métallurgie des poudres comporte au moins les étapes suivantes :

  • préparation des matières premières de la poudre inorganique;
  • granulation ;
  • mélange avec un liant organique pour obtenir la composition de moulage ou feedstock ;
  • pressage ou injection, notamment dans une chambre de moulage, d'une quantité du feedstock obtenu, pour la réalisation d'une ébauche de l'article, appelée pièce verte. L'injection est réalisée sous pression, notamment dans un injecteur à vis comportant des moyens de mise en température de ce feedstock;
  • étuvage de déliantage pour la combustion ou/et la dissolution de certains composants du liant organique pour obtenir un corps marron;
  • traitement thermique (frittage) de l'ébauche ou du corps marron en sortie de déliantage, donnant sa cohérence finale à l'article obtenu en cermet massif et dense. Ce traitement thermique entraîne un retrait dimensionnel, qui permet l'obtention d'un article en cotes finies;
  • traitement de finition d'aspect de l'article (usinage et/ou polissage).
More specifically, the overall process for manufacturing a solid cermet article produced by powder metallurgy comprises at least the following steps:
  • preparation of raw materials of inorganic powder;
  • granulation;
  • mixing with an organic binder to obtain the molding or feedstock composition;
  • pressing or injection, in particular in a molding chamber, of a quantity of the feedstock obtained, for the production of a blank of the article, called green part. The injection is carried out under pressure, in particular in a screw injector comprising means for bringing this feedstock to temperature;
  • debinding stoving for the combustion or / and the dissolution of certain components of the organic binder to obtain a brown body;
  • heat treatment (sintering) of the blank or of the brown body at the end of debinding, giving its final consistency to the article obtained in solid and dense cermet. This heat treatment results in dimensional shrinkage, which makes it possible to obtain an article in finished dimensions;
  • finishing treatment of the article's appearance (machining and / or polishing).

Dans l'habillage horloger, on utilise des cermets massifs à base de TiC, de TiCN ou de TiN pour leurs caractères «d'inrayabilité» (hautes duretés), pour leurs éclats métalliques après polissage se rapprochant de ceux des aciers et des aciers inoxydables (pour les bases TiC et TiCN) et pour leurs faibles masses volumiques, se rapprochant de celles des céramiques. Ces cermets montrent une excellente résistance à la corrosion saline. Toutefois, ils présentent l'inconvénient de tous utiliser comme liant métallique le nickel ou le cobalt et présentent donc des taux de libération en nickel ou cobalt non négligeables, pouvant parfois dépasser le taux maximum autorisé (0.280 µg/cm2.semaine selon les normes actuelles RoHS et REACH).In watchmaking, massive cermets based on TiC, TiCN or TiN are used for their "scratch-resistant" characteristics (high hardness), for their metal chips after polishing approaching those of steels and stainless steels. (for TiC and TiCN bases) and for their low densities, approaching those of ceramics. These cermets show excellent resistance to salt corrosion. However, they have the drawback of all using nickel or cobalt as metal binder and therefore exhibit non-negligible nickel or cobalt release rates, which can sometimes exceed the maximum authorized rate (0.280 µg / cm 2. Week according to standards. current RoHS and REACH).

Pour des applications en horlogerie, bijouterie et autres dispositifs électroniques portables, et spécialement pour des éléments de décors en contact avec la peau humaine, un matériau de type cermet doit absolument garantir l'absence de libération d'éléments allergènes. Les liants métalliques alternatifs proposés jusqu'à ce jour par les industriels actifs dans le domaine des cermets à base de TiC, de TiCN ou de TiN sont principalement le fer (Fe), le fer-chrome (Fe-Cr) et le fer-chrome-molybdène (Fe-Cr-Mo), les aciers inox et les aciers réfractaires. Ainsi du document US 3,725,016 , on connaît un cermet avec une matrice d'acier comprenant en poids jusqu'à 20% de chrome, de 1 à 5% de bore, de 2 à 8% de silicium, de 1.5 à 5% de carbone, jusqu'à 5% de molybdène, le reste étant du fer. Du document US 6,641,640 , on connaît un cermet avec un liant métallique à base d'un alliage de fer austénitique qui contient en poids moins de 0.5% de carbone, de 2 à 26% de manganèse, de 11 à 24% de chrome, de 2.5 à 10% de molybdène, moins de 8% de tungstène et de 0.55 à 1.2% d'azote.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. Thus from the document US 3,725,016 , we know a 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. Of the document US 6,641,640 , we know 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.

De plus, appliqués à un élément de décors horlogers, tous ces cermets présentent une résistance à la corrosion en immersion en milieu salin ainsi que sous brouillards salins qui est extrêmement faible, notamment après avoir subi des étapes d'usinages de terminaisons (mécanique, laser) et/ou de polissages.In addition, applied to an element of watchmaking decorations, 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.

Appliqués à un élément de mécanisme horloger, ces cermets sont intéressants pour leur haute dureté, mais leur faible résistance à la corrosion est préjudiciable en cas de présence de condensation à l'intérieur du mécanisme horloger ou pour des pièces d'habillage en contact avec la sueur du porteur.Applied to an element of a watch mechanism, 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.

Résumé de l'inventionSummary of the invention

La présente invention a pour but de remédier à ces inconvénients en proposant une composition de moulage par métallurgie des poudres permettant de fabriquer des articles, notamment des articles de décor ou d'habillage, en cermet massif fritté ne comportant pas d'éléments allergènes tels que le nickel et/ou le cobalt, traditionnellement utilisés.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.

Un autre but de la présente invention est de proposer une composition de moulage par métallurgie des poudres permettant de fabriquer des articles, notamment des articles de décor ou d'habillage et des éléments de mécanismes horlogers, en cermet massif fritté hautement résistants à la corrosion en immersion en milieu salin et sous brouillards salins.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.

Un autre but de la présente invention est de proposer une composition de moulage par métallurgie des poudres présentant par ailleurs les mêmes propriétés de dureté, de ténacité, de densité, d'éclat, et de teintes, que les cermets disponibles sur le marché pour la fabrication d'articles de décor ou d'habillage dans les domaines de l'horlogerie, de bijouterie, ou des appareils portables électroniques.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.

A cet effet, l'invention se rapporte tout d'abord à une composition de moulage par métallurgie des poudres destinée à la fabrication d'articles en cermet massif fritté, comprenant une poudre inorganique destinée à former le cermet et un liant organique.To this end, 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.

Selon l'invention, ladite poudre inorganique est constituée en poids de 35% à 95% d'au moins une phase céramique à base de céramique choisie parmi le groupe constitué de TiC, TiCN, TiN et leurs mélanges, et de 5% à 65% d'une phase métallique, ladite phase métallique étant constituée en poids d'au moins 40% de fer, de 15% à 45% de chrome, de 0.1% à 25% de molybdène, de 0.1% à 10% de silicium, de 0 à 10% de bore, et de 0 à 10% de niobium, les quantités respectives des éléments de la phase métallique étant telles que leur somme est égale à 100% en poids de la phase métallique.According to the invention, 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.

Une telle composition de moulage permet d'obtenir des articles en cermet massif fritté sans élément allergène tel que le nickel et/ou le cobalt, et hautement résistants à la corrosion saline. Ledit article peut être par exemple un article de décor ou d'habillage ou un élément de mécanisme horloger.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.

La présente invention concerne également un procédé de fabrication par métallurgie des poudres d'un article en cermet massif fritté comprenant une étape de préparation d'une composition de moulage telle que définie ci-dessus, une étape de moulage de ladite composition de moulage pour réaliser une pièce verte de l'article, puis des étapes de déliantage et de frittage pour obtenir ledit article en cermet massif fritté.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.

La présente invention concerne également un article de décor ou d'habillage en cermet massif fritté, dans lequel ledit cermet est obtenu à partir d'une poudre inorganique constituée en poids de 35% à 95% d'au moins une phase céramique à base de céramique choisie parmi le groupe constitué de TiC, TiCN, TiN et leurs mélanges, et de 5% à 65% d'une phase métallique, ladite phase métallique étant constituée en poids d'au moins 40% de fer, de 15% à 45% de chrome, de 0.1% à 25% de molybdène, de 0.1% à 10% de silicium, de 0 à 10% de bore, et de 0 à 10% de niobium, les quantités respectives des éléments de la phase métallique étant telles que leur somme est égale à 100% en poids de la phase métallique.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.

La présente invention concerne également un élément de mécanisme d'horlogerie en cermet massif fritté, dans lequel ledit cermet est obtenu à partir d'une poudre inorganique constituée en poids de 35% à 95% d'au moins une phase céramique à base de céramique choisie parmi le groupe constitué de TiC, TiCN, TiN et leurs mélanges, et de 5% à 65% d'une phase métallique, ladite phase métallique étant constituée en poids d'au moins 40% de fer, de 15% à 45% de chrome, de 0.1% à 25% de molybdène, de 0.1% à 10% de silicium, de 0 à 10% de bore, et de 0 à 10% de niobium, les quantités respectives des éléments de la phase métallique étant telles que leur somme est égale à 100% en poids de la phase métallique.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.

Description détaillée des modes de réalisation préférésDetailed description of the preferred embodiments

La composition de moulage par métallurgie des poudres selon l'invention comprend une poudre inorganique destinée à former un cermet et un liant organique.The powder metallurgy molding composition according to the invention comprises an inorganic powder intended to form a cermet and an organic binder.

Le liant organique utilisé dans la composition de moulage selon l'invention comprend de manière connue une base structurante polymère de type polyéthylène et/ou polypropylène et/ou copolymères, des cires de type paraffines pouvant être dissoutes à chaud dans des solvants organiques et/ou des polyéthylènes glycol pouvant être dissouts à chaud dans l'eau et au moins un surfactant organique de type acide stéarique ou stéarates. Des formulations de liants organiques plus complexes et donnant d'excellents résultats peuvent aussi être utilisées. De telles formulations sont par exemple décrites dans la demande internationale WO 2014/191304 . Pour la fabrication du feedstock c'est-à-dire le mélange à chaud des poudres organiques et inorganiques pour le moulage, on utilisera préférentiellement un malaxeur ou une extrudeuse à double vis. Plus spécifiquement, un malaxeur chauffant à couteaux rotatifs hautes vitesses, tel que décrit dans la demande EP 2801560 permet l'obtention d'un mélange intime et homogène des poudres d'organiques et d'inorganiques.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 . For the manufacture of the feedstock, that is to say the hot mixing of organic and inorganic powders for molding, 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.

De préférence, la composition de moulage selon l'invention comprend de 4% à 24% en poids de liant organique et 76% à 96% en poids de poudres inorganiques.Preferably, 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.

Ladite poudre inorganique est constituée en poids de 35% à 95% d'au moins une phase céramique et de 5% à 65% d'une phase métallique, de préférence de 50% à 90% de la phase céramique et de 10% à 50% de la phase métallique, plus préférentiellement de 65% à 85% de la phase céramique et de 15% à 35% de la phase métallique, et plus préférentiellement de 70% à 80% de la phase céramique et de 20% à 30% de la phase métallique.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.

La phase céramique de la poudre inorganique est à base de céramique choisie parmi le groupe constitué de TiC, TiCN, TiN et leurs mélanges. De préférence, la phase céramique est à base de TiC ou TiN.The ceramic phase of the inorganic powder is based on a ceramic chosen from the group consisting of TiC, TiCN, TiN and their mixtures. Preferably, the ceramic phase is based on TiC or TiN.

Dans la présente description, l'expression «phase céramique à base d'un élément » signifie que ladite phase céramique contient au moins 50% en poids dudit élément.In the present description, the expression “ceramic phase based on an element” means that said ceramic phase contains at least 50% by weight of said element.

Dans la présente description, tous les pourcentages sont indiqués en poids. D'une manière avantageuse, la phase céramique de la poudre inorganique est constituée en poids de 50% à 100% d'une phase céramique principale à base de céramique choisie parmi le groupe constitué de TiC, TiCN, TiN, et leurs mélanges, et de 0 à 50% d'au moins une phase céramique secondaire choisie parmi le groupe comprenant Cr3C2, CrN, NbC, NbN, TaC, TaN, et leurs mélanges.In the present description, all the percentages are given by weight. Advantageously, 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.

De préférence, la phase céramique de la poudre inorganique est constituée en poids de 80% à 100% de ladite phase céramique principale, et de 0 à 20% de ladite phase céramique secondaire, et plus préférentiellement de 90% à 100% de ladite phase céramique principale, et de 0 à 10% de ladite phase céramique secondaire.Preferably, 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.

Avantageusement, ladite phase céramique principale de la poudre inorganique peut être constituée uniquement de TiC ou être constituée de TiN, la phase céramique secondaire étant du NbN (par exemple 90/10).Advantageously, 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).

Selon l'invention, la phase métallique de la poudre inorganique est constituée en poids d'au moins 40% de fer, de 15% à 45% de chrome, de 0.1% à 25% de molybdène, de 0.1% à 10% de silicium, de 0 à 10% de bore, et de 0 à 10% de niobium, les quantités respectives des éléments de la phase métallique étant telles que leur somme est égale à 100% en poids de la phase métallique.According to the invention, 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.

De préférence, la phase métallique de la poudre inorganique est constituée majoritairement de fer et de chrome, et comprend en poids de préférence de 40% à 70% de fer, et plus préférentiellement de 45% à 60% de fer, et de 20% à 40% de chrome, et plus préférentiellement de 25% à 35% de chrome.Preferably, 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.

De préférence, la phase métallique de la poudre inorganique comprend en poids de 1% à 20% de molybdène, et plus préférentiellement de 5% à 10% de molybdène.Preferably, 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.

De préférence, la phase métallique de la poudre inorganique comprend en poids de 1% à 10% de silicium, et plus préférentiellement de 2% à 8% de silicium.Preferably, 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.

De préférence, la phase métallique de la poudre inorganique comprend en poids de 0% à 5% de bore, et plus préférentiellement de 0% à 1% de bore.Preferably, 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.

De préférence, la phase métallique de la poudre inorganique comprend en poids de 0% à 8% de niobium, et plus préférentiellement de 0% à 5% de niobium.Preferably, the metallic phase of the inorganic powder comprises by weight from 0% to 8% niobium, and more preferably from 0% to 5% niobium.

La phase métallique selon l'invention est donc un alliage constitué de Fe, Cr, Mo, Si et éventuellement de B et/ou Nb.The metal phase according to the invention is therefore an alloy consisting of Fe, Cr, Mo, Si and optionally of B and / or Nb.

Les teneurs préférées des différents éléments de la phase métallique de la poudre inorganique mentionnées ci-dessus peuvent être combinées entre elles pour autant que leur somme soit égale à 100% en poids de la phase métallique. Si besoin, le fer est utilisé pour faire le reste.The preferred contents of the various elements of the metallic phase of the inorganic powder mentioned above can be combined with one another provided that their sum is equal to 100% by weight of the metallic phase. If necessary, the iron is used to do the rest.

De préférence, la phase métallique de la poudre inorganique est constituée d'au moins 40% de fer (de préférence au moins 45% de fer), de 25% à 35% de chrome, de 5% à 10% de molybdène, de 2% à 8% de silicium, de 0% à 1% de bore, et 0% à 5% de niobium, les quantités respectives des éléments de la phase métallique étant telles que leur somme est égale à 100% en poids de la phase métallique.Preferably, 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.

D'une manière surprenante, la combinaison de Mo et Si dans la phase métallique Fe-Cr permet d'obtenir une bonne résistance à la corrosion en milieu salin.Surprisingly, 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.

L'addition de bore et/ou de niobium à la phase métallique Fe-Cr-Mo-Si permet d'augmenter la résistance à la corrosion en milieu salin. L'addition de bore permet également d'accroitre la ténacité du cermet.The addition of boron and / or niobium to the Fe-Cr-Mo-Si metallic phase makes it possible to increase the resistance to corrosion in a saline environment. The addition of boron also makes it possible to increase the tenacity of the cermet.

D'une manière particulièrement avantageuse, la composition de moulage de l'invention, et en particulier la phase métallique ne comprend ni nickel, ni cobalt. La phase métallique est également exempte de manganèse et de carbone.In a particularly advantageous manner, the molding composition of the invention, and in particular the metallic phase, contains neither nickel nor cobalt. The metallic phase is also free from manganese and carbon.

La présente invention concerne également un procédé de fabrication par métallurgie des poudres d'un article en cermet massif fritté comprenant une étape de préparation d'une composition de moulage telle que définie ci-dessus, une étape de moulage de ladite composition de moulage pour réaliser une pièce verte de l'article, puis des étapes de déliantage et de frittage pour obtenir ledit article en cermet massif fritté.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.

Plus précisément, l'étape de préparation d'une composition de moulage de l'invention comprend les pesées de la poudre de la phase céramique principale, éventuellement des poudres des phases céramiques secondaires, et des éléments constituant la phase métallique. Les poudres sont ensuite broyées, par exemple par ball-milling ou par attrition, afin d'obtenir une poudre inorganique destinée à former le cermet présentant une distribution homogène et comprenant des particules de taille moyenne finale de quelques microns. Les composants constituant le liant organique sont ensuite ajoutés pour obtenir la composition de moulage selon l'invention, appelée traditionnellement feedstock. Le feedstock peut être mis sous forme de poudre ou de granules pour être conservé jusqu'à la mise en œuvre de l'étape de moulage de la composition de moulage.More specifically, the step of preparing a molding composition of the invention comprises weighing the powder of the main ceramic phase, optionally of the powders of the secondary ceramic phases, and of the elements constituting the metallic phase. The powders are then ground, for example by ball-milling or by attrition, in order to obtain an inorganic powder intended to form the cermet having a homogeneous distribution and comprising particles of final average size of a few microns. The components constituting the organic binder are then added to obtain the molding composition according to the invention, traditionally called feedstock. The feedstock can be put in the form of powder or granules to be preserved until the implementation of the step of molding the molding composition.

Cette étape de moulage comprend typiquement une opération de moulage par pressage ou injection à chaud sous pression dans un moule avec cavités. On obtient une ébauche ou une pièce verte de l'article à réaliser. La pièce verte est refroidie dans la cavité puis est éjectée du moule.This molding step typically comprises a hot pressing or injection molding operation under pressure in a mold with cavities. We obtain a blank or a green part of the article to be produced. The green part is cooled in the cavity and then is ejected from the mold.

La pièce verte est ensuite déliantée, pour éliminer une partie des composants du liant organique, notamment les cires, avant l'étape de frittage. On obtient un corps marron.The green part is then debonded, to remove part of the components of the organic binder, in particular the waxes, before the sintering step. We get a brown body.

Pour l'étape de frittage, le corps marron est placé dans un four à haute température (par exemple 1350°C - 1550°C) pour obtenir un article en cermet massif fritté et dense.For the sintering step, the brown body is placed in a high temperature furnace (e.g. 1350 ° C - 1550 ° C) to obtain a dense sintered solid cermet article.

Le procédé comprend ensuite une étape de traitement de finition d'aspect de l'article, par usinage (mécanique, laser, jet d'eau, etc...) et/ou par polissage.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.

Un tel procédé de fabrication par métallurgie des poudres est connu de l'homme du métier et ne nécessite pas ici plus de détails.Such a method of manufacturing by powder metallurgy is known to those skilled in the art and does not require further details here.

L'article peut être un article de décor ou d'habillage d'horlogerie ou de bijouterie ou de décors d'appareils portables, ou encore un élément d'un mécanisme d'horlogerie.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.

La présente invention concerne également un article de décor ou d'habillage en cermet massif fritté, notamment un article de décor ou d'habillage obtenu par le procédé de fabrication par métallurgie des poudres utilisant la composition de moulage décrite ci-dessus. L'article de décor ou d'habillage selon l'invention est réalisé en cermet massif fritté, ledit cermet massif fritté ayant été obtenu à partir d'une poudre inorganique constituée en poids de 35% à 95% d'au moins une phase céramique à base de céramique choisie parmi le groupe constitué de TiC, TiCN, TiN et leurs mélanges, et de 5% à 65% d'une phase métallique, ladite phase métallique étant constituée en poids d'au moins 40% de fer, de 15% à 45% de chrome, de 0.1% à 25% de molybdène, de 0.1% à 10% de silicium, de 0 à 10% de bore, et de 0 à 10% de niobium, les quantités respectives des éléments de la phase métallique étant telles que leur somme est égale à 100% en poids de la phase métallique.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.

La présente invention concerne enfin un élément d'un mécanisme horloger en cermet massif fritté, notamment un élément d'un mécanisme horloger obtenu par le procédé de fabrication par métallurgie des poudres utilisant la composition de moulage décrite ci-dessus. L'élément d'un mécanisme horloger selon l'invention est réalisé en cermet massif fritté, ledit cermet massif fritté ayant été obtenu à partir d'une poudre inorganique constituée en poids de 35% à 95% d'au moins une phase céramique à base de céramique choisie parmi le groupe constitué de TiC, TiCN, TiN et leurs mélanges, et de 5% à 65% d'une phase métallique, ladite phase métallique étant constituée en poids d'au moins 40% de fer, de 15% à 45% de chrome, de 0.1% à 25% de molybdène, de 0.1% à 10% de silicium, de 0 à 10% de bore, et de 0 à 10% de niobium, les quantités respectives des éléments de la phase métallique étant telles que leur somme est égale à 100% en poids de la phase métallique.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 .

La composition finale du cermet massif fritté dépendant des paramètres de frittage utilisés (température, durée du palier de frittage, pression dans l'enceinte de frittage), il est préférable ici de caractériser l'article de décor ou d'habillage ou l'élément d'un mécanisme d'horlogerie de l'invention par la composition du cermet avant frittage.As 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.

La composition de moulage de l'invention permet d'obtenir, par métallurgie des poudres, des articles en cermet massif fritté, notamment des articles de décor ou d'habillage, exempts des éléments allergènes traditionnellement utilisés dans les cermets, tels que le nickel ou le 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, free from the allergenic elements traditionally used in cermets, such as nickel or cobalt.

De plus, la composition de moulage de l'invention permet d'obtenir, par métallurgie des poudres, des articles en cermet massif fritté, notamment de articles de décor ou d'habillage ou des éléments de mécanisme horloger, hautement résistants à la corrosion en milieu salin, même après avoir subi un traitement de finition.In addition, 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.

En outre, les articles de décor ou d'habillage ou les éléments de mécanisme horloger en cermet massif fritté de l'invention présentent une dureté comprise entre 1000 et 1800 Vickers, et sont donc particulièrement résistants aux rayures, de manière similaire aux cermets traditionnellement utilisés.In addition, 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. .

Ils présentent également une ténacité suffisante pour être facilement usinables et polissables, de manière similaire aux cermets comprenant du nickel ou du cobalt traditionnellement utilisés.They also have sufficient tenacity to be easily machinable and polishable, in a manner similar to cermets comprising nickel or cobalt conventionally used.

Les différents éléments utilisés pour réaliser les articles de décor ou d'habillage de l'invention permettent d'obtenir des cermets massifs frittés de faibles densités, soit de masses volumiques inférieures à 10 g/cm3. Les articles de décor ou d'habillage de l'invention présentent donc un confort au porté agréable, notamment lorsqu'ils concernent des articles d'horlogerie et consistent par exemple en des coiffes, des carrures, des boites de montre ou des bracelets.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.

Les articles de décor ou d'habillage en cermet massif fritté de l'invention présentent, après polissage, un bel éclat métallique, comme les cermets traditionnellement utilisés.The decorative or covering articles in sintered solid cermet of the invention exhibit, after polishing, a beautiful metallic luster, like the cermets traditionally used.

Les articles de décor ou d'habillage en cermet massif fritté de l'invention présentent des teintes blanches à grises et gris-rose à rose pour les cermets à base de TiC et TiCN, et des teintes jaunes à jaune-bronze pour les cermets à base de TiN.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.

Les articles de décor ou d'habillage en cermet massif fritté de l'invention sont des articles de décor ou d'habillage d'horlogerie ou de bijouterie, ainsi que des articles d'habillage ou de protection de dispositifs électroniques portables, tels que les téléphones portables et les tablettes.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.

Les éléments de mécanisme d'horlogerie en cermet massif fritté de l'invention sont notamment des éléments fonctionnels. Ces éléments selon l'invention présentent une haute dureté et sont résistants à la corrosion en cas de présence de condensation à l'intérieur du mécanisme d'horlogerie. Un tel élément peut être par exemple une platine. Cet élément est réalisé traditionnellement à partir de laiton massif dans lequel sont usinés des trous permettant le chassage de rubis comportant en leur centre un trou de faible diamètre pour l'insertion de pivots d'axes. Ce laiton doit ensuite être protégé de la corrosion par un dépôt en surface de nickel. Une platine en cermet massif selon l'invention, présentant une haute dureté, et réalisée selon des procédés de moulage par pression ou par injection conformément au procédé de fabrication de l'invention, permet l'insertion directe des pivots d'axes, sans chassage ni utilisation de rubis et ne nécessite pas de recourir à un traitement de surface pour la protéger de la corrosion.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.

La présente invention sera maintenant illustrée plus en détails par les exemples non limitatifs qui suivent.The present invention will now be illustrated in more detail by the non-limiting examples which follow.

Exemples 1 à 10Examples 1 to 10

Des articles en cermet massif fritté sont réalisés à partir de compositions de moulage comprenant les différentes poudres inorganiques indiquées dans le tableau I ci-dessous, et comme liant organique un liant comprenant un polyéthylène comme organique structurant, une cire de paraffine se dissolvant à chaud dans l'heptane, dans l'éthanol ou dans l'isopropanol, et comme surfactant de l'acide stéarique.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.

Les poudres inorganiques comportent toutes en poids 70% d'une phase céramique constituée à 100% de TiC et 30% d'une phase métallique comprenant nominalement en poids au moins du fer et 28% de chrome avant frittage.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.

A titre comparatif, on fabrique différents articles pour lesquels la phase métallique Fe-Cr ne contient pas de molybdène ou pas de silicium (exemples 1 à 9).By way of comparison, various articles are manufactured for which the Fe-Cr metal phase does not contain molybdenum or does not contain silicon (examples 1 to 9).

On réalise de la même manière un article selon l'invention dans lequel la phase métallique Fe-Cr contient à la fois du molybdène et du silicium (exemple 10).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).

Les articles sont obtenus selon le procédé suivant :

  • broyage du mélange des poudres de la phase céramique et de la phase métallique par ball-milling permettant une réduction significative des tailles de particules tout en assurant une bonne homogénéité du mélange après broyage afin de constituer la poudre inorganique
  • fabrication du mélange du liant organique et de la poudre inorganique par malaxage à chaud en utilisant préférentiellement un malaxeur à couteaux hautes vitesses
  • moulage par injection de pièces 3D pour l'obtention de pièces vertes (« green body »)
  • décirage à chaud dans l'heptane à 70°C et durant 24h des pièces vertes pour dissoudre la paraffine et une fraction du surfactant présents dans le liant organique
  • déliantage thermique à une température d'au moins 600°C du composé organique structurant de type polyéthylène et des résidus de surfactant pour obtenir un corps marron (« brown body »)
  • frittage sous gaz inerte (argon) du corps marron à une température d'au moins 1450°C afin d'obtenir un cermet massif dense fritté.
The articles are obtained according to the following process:
  • grinding of the mixture of powders of the ceramic phase and of the metallic phase by ball-milling allowing a significant reduction of the particle sizes while ensuring good homogeneity of the mixture after grinding in order to constitute the inorganic powder
  • manufacture of the mixture of the organic binder and the inorganic powder by hot kneading, preferably using a high-speed knife kneader
  • injection molding of 3D parts to obtain green parts ("green body")
  • hot dewaxing in heptane at 70 ° C and for 24 hours green parts to dissolve the paraffin and a fraction of the surfactant present in the organic binder
  • thermal debinding at a temperature of at least 600 ° C of the structuring organic compound of polyethylene type and of the surfactant residues to obtain a "brown body"
  • sintering under inert gas (argon) of the brown body at a temperature of at least 1450 ° C in order to obtain a dense sintered solid cermet.

Les pièces brutes de frittage sont ensuite usinées et polies mécaniquement ou en vrac pour l'obtention de pièces finales.The sintered parts are then machined and polished mechanically or in bulk to obtain final parts.

Pour chaque article des exemples 1 à 10, on mesure la dureté, la ténacité, le taux de porosité et la résistance à la corrosion.For each article of Examples 1 to 10, the hardness, toughness, porosity rate and corrosion resistance were measured.

La dureté est mesurée à l'aide d'un duromètre Wolpert muni d'une pointe Vickers (pyramide à base carrée) et sous une charge appliquée de 30 kg. Au préalable un étalonnage est réalisé sur un étalon référencé de dureté comparable à celle des cermets.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.

La dureté doit être comprise entre 1000 et 1800 Vickers.The hardness should be between 1000 and 1800 Vickers.

Pour les mesures de ténacités, celles-ci sont extrapolées à partir de la taille des fissures se développant aux quatre coins de l'empreinte de dureté.For toughness measurements, these are extrapolated from the size of the cracks developing at the four corners of the hardness indentation.

La valeur de ténacité représente la capacité d'un matériau à résister à la propagation d'une fissure consécutivement à un choc. Pour les céramiques traditionnellement utilisées comme décors horlogers comme la zircone, notamment pour la réalisation d'une boite de montre, on considère que la ténacité mesurée par indentations Vickers doit être au minimum de 4.5 MPa.m1/2.The toughness value represents the ability of a material to resist the propagation of a crack following an impact. For ceramics traditionally used as horological decorations such as zirconia, in particular for the production of a watch case, it is considered that the toughness measured by Vickers indentations must be at least 4.5 MPa.m 1/2 .

Le taux de porosité est estimé à l'aide d'un logiciel d'acquisition d'image permettant de discriminer sur une surface polie et à un grossissement de 100x, les différentes zones de contraste. La porosité mesurée est donc une porosité surfacique. Un taux de porosité faible est directement lié à une bonne qualité et à un bel éclat de la surface après polissage.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.

La résistance à la corrosion est mesurée à l'aide d'une enceinte de brouillard salin certifiée (ASCOTT S120XP) dans laquelle l'échantillon est positionné de manière incliné et va ensuite subir un brouillard salin (5% NaCl) durant 72h, à la température de 35°C.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.

Les résultats obtenus sont indiqués dans le tableau I ci-dessous : Tableau I Ex. Composition de la poudre inorganique avant frittage Dureté (HV30) Ténacité (MPa.m1/2) Taux de porosité (%) Résistance à la corrosion 1 70TiC-FeCr28 1487 9.2 0.08 faible 2 70TiC-FeCr28Mo16 1612 7.4 0.17 faible 3 70TiC-FeCr28Mo12 1593 7.3 0.14 faible 4 70TiC-FeCr28Mo8 1578 8.6 0.09 faible 5 70TiC-FeCr28Mo4 1555 9.0 0.53 faible 6 70TiC-FeCr28Si1 1486 8.1 0.34 faible 7 70TiC-FeCr28Si2 1396 8.5 0.10 faible 8 70TiC-FeCr28Si3 1448 7.4 0.29 faible 9 70TiC-FeCr28Si4 1362 8.1 0.12 faible 10 70TiC-FeCr28Mo8Si4 1481 6.1 0.13 bonne The results obtained are shown in Table I below: Table I Ex. Composition of the inorganic powder before sintering Hardness (HV 30 ) Tenacity (MPa.m 1/2 ) Porosity rate (%) Corrosion resistance 1 70TiC-FeCr28 1487 9.2 0.08 low 2 70TiC-FeCr28Mo16 1612 7.4 0.17 low 3 70TiC-FeCr28Mo12 1593 7.3 0.14 low 4 70TiC-FeCr28Mo8 1578 8.6 0.09 low 5 70TiC-FeCr28Mo4 1555 9.0 0.53 low 6 70TiC-FeCr28Si1 1486 8.1 0.34 low 7 70TiC-FeCr28Si2 1396 8.5 0.10 low 8 70TiC-FeCr28Si3 1448 7.4 0.29 low 9 70TiC-FeCr28Si4 1362 8.1 0.12 low 10 70TiC-FeCr28Mo8Si4 1481 6.1 0.13 good

Les résultats du tableau I montrent que seule la composition de moulage selon l'invention (Exemple 10) comprenant une phase métallique Fe-Cr-Mo-Si permet d'obtenir un article en cermet massif fritté, sans nickel ni cobalt, présentant une bonne résistance à la corrosion en milieu salin. Les exemples comparatifs (Exemples 1 à 9) sans Mo ou sans Si ne présentent qu'une faible résistance à la corrosion en milieu salin.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.

Exemples 11-13Examples 11-13

On réalise des articles selon l'invention conformément au procédé des exemples 1 à 10. Les poudres inorganiques comportent toutes en poids 70% d'une phase céramique constituée à 100% de TiC et 30% d'une phase métallique constituée nominalement en poids de fer, 28% de chrome, 8% de molybdène, 4% de silicium et de 0.2% à 0.6% de bore avant frittage.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.

On réalise les mêmes mesures que pour les exemples 1 à 10.The same measurements are carried out as for Examples 1 to 10.

Les résultats sont indiqués dans le tableau II ci-dessous : Tableau II Ex. Composition de la poudre inorganique avant frittage Dureté (HV30) Ténacité (MPa.m1/2) Taux de porosité (%) Résistance à la corrosion 11 70TiC-FeCr28Mo8Si4B0.2 1441 7.2 1.58 Très bonne 12 70TiC-FeCr28Mo8Si4B0.4 1444 7.7 3.01 Très bonne 13 70TiC-FeCr28Mo8Si4B0.6 1422 7.9 1.55 Très bonne The results are shown in Table II below: 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

Les exemples 11 à 13 de l'invention montrent que l'ajout d'une faible quantité de bore permet d'accroitre la résistance à la corrosion en milieu salin. En outre, l'ajout de bore permet d'augmenter la ténacité. Ainsi la ténacité mesurée de 6.1 MPa.m1/2 pour l'exemple 10 de l'invention, sans bore, passe à la valeur maximale de 7.9 MPa.m1/2 pour l'exemple 13 de l'invention, comprenant une quantité massique nominale de 0.6% de bore.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. In addition, the addition of boron increases toughness. Thus 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.

Exemple 14Example 14

On réalise un article selon l'invention conformément au procédé des exemples 1 à 10. La poudre inorganique comporte en poids 75% d'une phase céramique constituée à 100% de TiC et 25% d'une phase métallique constituée nominalement en poids de 49.6% de fer, 34% de chrome, 8% de molybdène, 4% de silicium, 4% de niobium et 0.4% de bore avant frittage.An article according to the invention is produced according to the process of Examples 1 to 10. 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.

On réalise les mêmes mesures que pour les exemples 1 à 10.The same measurements are carried out as for Examples 1 to 10.

Les résultats sont indiqués dans le tableau III ci-dessous : Tableau III Ex. Composition de la poudre inorganique avant frittage Dureté (HV30) Ténacité (MPa.m1/2) Taux de porosité (%) Résistance à la corrosion 14 75TiC-FeCr34Mo8Si4Nb4B0.4 1528 6.4 0.39 Très bonne The results are shown in Table III below: 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

L'exemple 14 de l'invention montre que l'ajout de niobium permet également d'accroitre la résistance à la corrosion en milieu salin. En outre, l'ajout de niobium permet d'améliorer l'homogénéité de la phase métallique et ainsi de diminuer la porosité et d'augmenter la dureté du cermet obtenu.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. In addition, 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.

Exemple 15Example 15

On réalise un article selon l'invention conformément au procédé des exemples 1 à 10. La poudre inorganique comporte en poids 80% d'une phase céramique constituée nominalement en poids de 90% de TiN (phase céramique principale) et de 10% de NbN (phase céramique secondaire), et 20% d'une phase métallique constituée nominalement en poids de 59% de fer, 28% de chrome, 8% de molybdène, et 5% de silicium, avant frittage.An article according to the invention is produced in accordance with the process of Examples 1 to 10. 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.

On mesure la dureté, et la résistance à la corrosion comme pour les exemples 1 à 10.The hardness and the corrosion resistance are measured as for Examples 1 to 10.

Les résultats sont indiqués dans le tableau IV ci-dessous : Tableau IV Ex. Composition de la poudre inorganique avant frittage Dureté (HV30) Résistance à la corrosion 15 TiN-10NbN-FeCr28Mo8Si5 1108 bonne The results are shown in Table IV below: Table IV Ex. Composition of the inorganic powder before sintering Hardness (HV 30 ) Corrosion resistance 15 TiN-10NbN-FeCr28Mo8Si5 1108 good

L'exemple 15 de l'invention comprenant une phase céramique principale TiN et une phase céramique secondaire NbN, ainsi qu'une phase métallique Fe-Cr-Mo-Si présente une bonne résistance à la corrosion en milieu salin.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.

L'article en cermet massif fritté obtenu présente un éclat métallique après polissage de teint jaune « bronze » avec des indices de colorimétrie L*=74.1, a*=5.1, b*=20.2 mesurés à l'aide d'un spectrophotomètre Konica Minolta CM-3610 permettant d'effectuer des mesures de colorimétrie en réflectance dans l'espace de référence L*a*b. Avant chaque mesure, une calibration est faite sur un échantillon de référence puis trois mesures sont alors réalisées successivement.The solid sintered cermet article obtained exhibits a metallic luster after polishing with a "bronze" yellow complexion with colorimetry indices L * = 74.1, a * = 5.1, b * = 20.2 measured using a Konica Minolta spectrophotometer CM-3610 for performing reflectance colorimetry measurements in the L * a * b reference space. Before each measurement, a calibration is made on a reference sample then three measurements are then carried out successively.

Claims (14)

  1. Powder metallurgy moulding composition intended for manufacturing decorative or covering articles or an element of a watch movement in sintered massive cermet, comprising an inorganic powder intended to form the cermet and an organic binder, characterized in that said inorganic powder consists 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% 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 amounts of the elements of the metallic phase being such that their sum is equal to 100 wt% of the metallic phase.
  2. Moulding composition according to Claim 1, characterized in that the metallic phase comprises by weight from 40% to 70% of iron, preferably from 45% to 60% of iron.
  3. Moulding composition according to one of the preceding claims, characterized in that the metallic phase comprises by weight from 20% to 40% of chromium, and preferably from 25% to 35% of chromium.
  4. Moulding composition according to one of the preceding claims, characterized in that the metallic phase comprises by weight from 1% to 20% of molybdenum, and preferably from 5% to 10% of molybdenum.
  5. Moulding composition according to one of the preceding claims, characterized in that the metallic phase comprises by weight from 1% to 10% of silicon, and preferably from 2% to 8% of silicon.
  6. Moulding composition according to one of the preceding claims, characterized in that the metallic phase comprises by weight from 0% to 5% of boron, and preferably from 0% to 1% of boron.
  7. Moulding composition according to one of the preceding claims, characterized in that the metallic phase comprises by weight from 0% to 8% of niobium, and preferably from 0% to 5% of niobium.
  8. Moulding composition according to one of the preceding claims, characterized in that the ceramic phase consists by weight of 50% to 100% of a principal ceramic phase based on ceramic selected from the group consisting of TiC, TiCN, TiN, and mixtures thereof, and from 0 to 50% of at least one secondary ceramic phase selected from the group comprising Cr3C2, CrN, NbC, NbN, TaC, TaN, and mixtures thereof.
  9. Moulding composition according to one of the preceding claims, characterized in that said inorganic powder consists by weight of 50% to 90% of the ceramic phase and from 10% to 50% of the metallic phase, and preferably from 65% to 85% of the ceramic phase and from 15% to 35% of the metallic phase.
  10. Moulding composition according to one of the preceding claims, characterized in that it comprises by weight from 76% to 96% of inorganic powder and from 4% to 24% of organic binder.
  11. Method based on powder metallurgy for manufacturing an article in sintered massive cermet comprising a step of preparing a moulding composition according to one of Claims 1 to 10, a step of moulding said moulding composition for making a green compact of the article, and then steps of binder removal and sintering to obtain said article in sintered massive cermet.
  12. Method based on powder metallurgy for manufacturing an article in sintered massive cermet according to Claim 11, characterized in that said article is a decorative or covering article.
  13. Method based on powder metallurgy for manufacturing an article in sintered massive cermet according to Claim 11, characterized in that said article is an element of a clock or watch movement.
  14. Decorative or covering article or an element of a watch mouvement in sintered massive cermet, characterized in that said sintered massive 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% 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 amounts of the elements of the metallic phase being such that their sum is equal to 100 wt% of the metallic phase.
EP17200647.0A 2017-11-08 2017-11-08 Moulding composition by powder metallurgy, especially for producing sintered solid cermet lining or decorative articles and said sintered solid cermet lining or decorative articles Active EP3482850B1 (en)

Priority Applications (4)

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EP17200647.0A EP3482850B1 (en) 2017-11-08 2017-11-08 Moulding composition by powder metallurgy, especially for producing sintered solid cermet lining or decorative articles and said sintered solid cermet lining or decorative articles
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 (en) 2017-11-08 2018-10-24 Powder metallurgy molding compositions and decorative or coated articles made of massive sintered cermet specifically intended to produce decorative or coated articles made of massive sintered cermet.
CN201811324644.0A CN109750206B (en) 2017-11-08 2018-11-08 Powder metallurgical moulding composition for producing decorative or covering articles in the form of sintered bulk cermets and said articles

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CN110435346B (en) * 2019-07-18 2021-11-19 广州番禺职业技术学院 Gold and silver staggered craft ornament and manufacturing method thereof
EP3943630A1 (en) 2020-07-22 2022-01-26 The Swatch Group Research and Development Ltd Cermet component for watchmaking or jewellery

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US3725016A (en) * 1972-01-24 1973-04-03 Chromalloy American Corp Titanium carbide hard-facing steel-base composition
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 (en) * 1986-02-20 1994-03-09 日立金属株式会社 Toughness
JPH0483805A (en) * 1990-07-25 1992-03-17 Sumitomo Electric Ind Ltd Combined hard alloy material
JPH0726173B2 (en) * 1991-02-13 1995-03-22 東芝タンガロイ株式会社 High toughness cermet and method for producing the same
DE19855422A1 (en) * 1998-12-01 2000-06-08 Basf Ag Hard material sintered part with a nickel- and cobalt-free, nitrogen-containing steel as a binder of the hard material phase
US20050211475A1 (en) * 2004-04-28 2005-09-29 Mirchandani Prakash K Earth-boring bits
WO2009067178A1 (en) * 2007-11-20 2009-05-28 Exxonmobil Research And Engineering Company Bimodal and multimodal dense boride cermets with low melting point binder
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US20190136352A1 (en) 2019-05-09
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CN109750206B (en) 2021-06-29
JP6764914B2 (en) 2020-10-07

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