EP3040790A1 - Timepiece or piece of jewellery made of a light titanium-based precious alloy - Google Patents

Timepiece or piece of jewellery made of a light titanium-based precious alloy Download PDF

Info

Publication number
EP3040790A1
EP3040790A1 EP14200381.3A EP14200381A EP3040790A1 EP 3040790 A1 EP3040790 A1 EP 3040790A1 EP 14200381 A EP14200381 A EP 14200381A EP 3040790 A1 EP3040790 A1 EP 3040790A1
Authority
EP
European Patent Office
Prior art keywords
atomic
alloy
composition
obeys
atomique
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14200381.3A
Other languages
German (de)
French (fr)
Inventor
Gaëtan Villard
Denis Vincent
Stéphane Lauper
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Montres Breguet SA
Original Assignee
Montres Breguet SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Montres Breguet SA filed Critical Montres Breguet SA
Priority to EP14200381.3A priority Critical patent/EP3040790A1/en
Priority to EP15817229.6A priority patent/EP3240915B1/en
Priority to CN201580028804.5A priority patent/CN106460094B/en
Priority to PCT/EP2015/080211 priority patent/WO2016107752A1/en
Priority to JP2017507083A priority patent/JP6389561B2/en
Priority to PCT/EP2015/080270 priority patent/WO2016107755A1/en
Priority to US15/308,185 priority patent/US10136708B2/en
Priority to EP15810677.3A priority patent/EP3241078B1/en
Priority to CN201580071445.1A priority patent/CN107208187B/en
Priority to US15/533,471 priority patent/US10206465B2/en
Priority to JP2017546041A priority patent/JP6514354B2/en
Publication of EP3040790A1 publication Critical patent/EP3040790A1/en
Priority to HK18103140.3A priority patent/HK1243743B/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • A44C27/003—Metallic alloys
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/02—Alloys based on gold
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • 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

Definitions

  • the invention relates to a cladding component for a timepiece or jewelery, made of a precious precious alloy based on titanium.
  • the invention also relates to a timepiece or jewelery comprising at least one such dressing component.
  • the invention relates to the field of timepieces for clocks, jewelery, or jewelry.
  • a characteristic common to most precious alloys used in watchmaking is their relatively high density (> 10 g / cm 3 ). Indeed, the two main precious metals used in watchmaking, namely gold and platinum, have respective densities of about 19.3 and 21.5 g / cm 3 . This has the consequence of making their alloys relatively heavy. Silver and palladium are lighter (10.5 and 12 g / cm 3 respectively) but much less used in watchmaking.
  • WO 2012/119647 A1 describes ceramic-precious metal composites that can reach relatively low densities ( ⁇ 8 g / cm 3 ).
  • the equi-atomic Ti phases (Pd / Pt / Au). Indeed, these phases may be similar to the TiNi equi-atomic phase used in some shape memory alloys.
  • the TiPd, TiPt and TiAu equi-atomic phases have a certain ductility and can, under certain conditions, present behaviors typical of TiNi shape memory alloys.
  • the TiPd, TiPt and TiAu equi-atomic alloys have been known for a long time and have been the subject of several studies involving high-temperature shape-memory alloys.
  • TiPd and TiAu alloys are titrable and therefore of interest for watchmaking and jewelery as particularly precious precious metals.
  • the invention proposes to make watchmaking components, both valuable to benefit the title and the resistance over time and corrosion, and lighter than known alloys.
  • the invention relates to a trim component for a timepiece or jewelery, made of a precious light alloy based on titanium, characterized in that said alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd 1-ay , with 0.3 ⁇ a ⁇ 0.6, 0 ⁇ x ⁇ 0.15, 0.01 ⁇ y ⁇ 0.4, and M being one or more of a first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.
  • said alloy obeys the atomic composition Ti ax (Zr, Hf) ⁇ M y Pd z , with 0.44 ⁇ a ⁇ 0.55; 0 ⁇ x ⁇ 0.05; 0.07 ⁇ y ⁇ 0.28; 0.25 ⁇ z ⁇ 0.45.
  • the invention also relates to a timepiece or jewelery comprising at least one such dressing component.
  • the invention is concerned with the replacement of gold and palladium in titanium-based alloys.
  • the invention relates to a dressing component 1 of watches or jewelery (including jewelery) precious alloy light titanium base, and any timepiece or jewelry including such a component.
  • alloys as described above in Table 1, which are overloaded with precious metal with respect to the titles to which they can be punched, generates an unnecessary extra cost.
  • advantageous substitutes may be suitable for the overloading of precious metal, and in particular the metals of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo , Ta, W.
  • the elements of a third group comprising: Cr, Mn, Cu, Zn and Ag can be introduced in a limited amount ( ⁇ 10 at%) in the TiPd and TiAu alloys instead of palladium and gold, respectively.
  • the elements of a fourth group comprising: Al, Si, Ge, Sn, Sb and In can be introduced in small quantities ( ⁇ 4 at%) in TiPd and TiAu alloys in place of titanium or palladium and gold, respectively.
  • substitute materials should not generate health risks.
  • the substitute materials of the latter must not be valuable.
  • the substitute materials in order not to overload the alloy, the substitute materials, ideally, are not heavier than the substituted metal.
  • a particularly advantageous embodiment of the invention relates to the substitution of a part of the palladium in a TiPd alloy.
  • the invention thus relates to a ductile alloy based on the Ti-Pd equi-atomic intermetallic, in which the excess of palladium relative to the mass content of Pd500 is partially or totally replaced by a non-precious element, so that the titanium still represents 50 atomic% of the final alloy.
  • a ductile alloy based on the Ti-Pd equi-atomic intermetallic, in which the excess of palladium relative to the mass content of Pd500 is partially or totally replaced by a non-precious element, so that the titanium still represents 50 atomic% of the final alloy.
  • Such an alloy has sufficient ductility to provide a formability similar to that of conventional titanium alloys.
  • TiPdFe and TiPdNb ternary alloys make it possible to attain the desired title.
  • TiPdNb alloys do not exhibit a parasitic shape memory effect, which is advantageous.
  • composition of the alloy may be formulated according to one of the following compositions, in which all the fractions are atomic:
  • Ti ax (Zr, Hf) x M y Pd 1-ay 0.3 ⁇ a ⁇ 0.6; 0 ⁇ x ⁇ 0.15; 0.01 ⁇ y ⁇ 0.4 M one or more of a first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, If, Ge, Sn, Sb, In. a defines the offset with respect to the equi-atomic composition.
  • x defines the degree of replacement of titanium by Zr and Hf. defines the fraction of substitution element.
  • Composition according to the fifth composition and for which M comprises Fe and / or Nb as majority elements.
  • composition according to the sixth composition and containing 50% by weight of palladium.
  • Ti49.7Pd32Fe15.3Cr3 atomic composition has interesting characteristics: low memory effect, low second phase quantity, and not too high mechanical properties.
  • compositions of this ninth composition containing atomically 12.5 and 10.5% of niobium exhibit a shape memory effect while the composition Ti 50 Pd 35.5 Nb 14.5 of the figure 1 containing 14.5% niobium has no effect of this kind.
  • This 14.5% niobium composition makes it possible to overcome these effects thanks to its two-phase nature.
  • compositions in particular as regards titanium, of the order of 0.3% of the total, do not fundamentally change the properties of these various compositions, and do not affect their ability to replace alloys. classics.
  • the invention thus relates to a cladding component for a timepiece or jewelery, made of a precious precious alloy based on titanium.
  • the composition of this alloy obeys the atomic composition: Ti ax (Zr, Hf) x M y Pd 1-ay , with 0.3 ⁇ a ⁇ 0.6, 0 ⁇ x ⁇ 0.15, 0.01 ⁇ y ⁇ 0.4, and M being one or more of a first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al , Si, Ge, Sn, Sb, In.
  • this alloy comprises between 15 and 60 atomic% of titanium, between 0 and 69 atomic% of palladium, between 1 and 40 atomic% of gold, and the complement at 100 atomic% comprises a total included between 0 and 15% atomic composition of zirconium and hafnium, and one or more components selected from a subgroup of the first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Pt, Cr, Mn , Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.
  • the alloy comprises in atomic% more palladium than gold.
  • the alloy comprises between 30% and 60% by weight of titanium, and the remainder of said alloy comprises a majority of palladium, and, in an amount greater than 10% by weight of the total of the alloy, at least one metal of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.
  • the alloy comprises between 30% and 60% by weight of titanium, and the remainder of this alloy comprises a majority of gold, and, in an amount greater than 10% by weight of the total of the alloy, at least a metal of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.
  • the alloy comprises at least one metal of a third group comprising: Cr, Mn, Cu, Zn and Ag, the total quantity of the metals of said third group is less than 10 atomic% of the total of the alloy .
  • the alloy comprises at least one metal of a fourth group comprising: Al, Si, Ge, Sn, Sb and In, the overall quantity of the metals of the fourth group is less than 4 atomic% of the total of the alloy.
  • the alloy has between 49.0 and 51.0 at% titanium.
  • the total atomic% of titanium, zirconium and hafnium is between 49.0 and 51.0 at%.
  • the alloy obeys the atomic composition Ti ax (Zr, Hf) ⁇ M y Pd 1-ay , with 0.3 ⁇ a ⁇ 0.6; 0 ⁇ x ⁇ 0.05; 0.01 ⁇ y ⁇ 0.4.
  • the alloy obeys the atomic composition Ti ax (Zr, Hf) ⁇ M y Pd z , with 0.3 ⁇ a ⁇ 0.6; 0 ⁇ x ⁇ 0.05; 0.01 ⁇ y ⁇ 0.4; 0.2 ⁇ z ⁇ 0.55.
  • the alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd z , with 0.44 ⁇ a ⁇ 0.55; 0 ⁇ x ⁇ 0.05; 0.07 ⁇ y ⁇ 0.28; 0.25 ⁇ z ⁇ 0.45.
  • M comprises one or more elements taken from a fifth group comprising: Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.
  • M comprises Fe and / or Nb as majority elements.
  • the alloy comprises 50% by weight of palladium.
  • the invention also relates to a timepiece 10 or jewelery, including a watch, comprising at least one such dressing component 1.
  • the various alloys selected above are ductile, and therefore allow shaping by the usual methods of deformation.
  • alloys with substitution components according to the invention makes it possible, again, to eliminate the shape memory effect observed in most of the base alloys described.
  • the alloy Ti 0.5 Pd 0.354 Nb 0.146 has an almost zero shape memory effect.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Adornments (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)
  • Powder Metallurgy (AREA)

Abstract

Composant d'habillage (1) pour pièce d'horlogerie ou de bijouterie, réalisé en alliage précieux léger à base de titane, où cet alliage obéit à la composition atomique Ti a-x (Zr,Hf) x M y Pd 1-a-y , avec 0.3<a<0.6, 0<x<0.15, 0.01<y<0.4, et M étant un ou plusieurs parmi un premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In. Pièce d'horlogerie (10) ou de bijouterie comportant au moins un tel composant d'habillage (1).A trim component (1) for a timepiece or a jewelery piece, made of a light titanium alloy, where this alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd 1-ay, with 0.3 <a <0.6, 0 <x <0.15, 0.01 <y <0.4, and M being one or more of a first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh , Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In. Timepiece (10) or jewelery having at least one such dressing component (1) ).

Description

Domaine de l'inventionField of the invention

L'invention concerne un composant d'habillage pour pièce d'horlogerie ou de bijouterie, réalisé en alliage précieux léger à base de titane.The invention relates to a cladding component for a timepiece or jewelery, made of a precious precious alloy based on titanium.

L'invention concerne encore une pièce d'horlogerie ou de bijouterie comportant au moins un tel composant d'habillage.The invention also relates to a timepiece or jewelery comprising at least one such dressing component.

L'invention concerne le domaine des pièces d'habillage d'horlogerie, de bijouterie, ou de joaillerie.The invention relates to the field of timepieces for clocks, jewelery, or jewelry.

Arrière-plan de l'inventionBackground of the invention

Une caractéristique commune à la plupart des alliages précieux utilisés en horlogerie est leur masse volumique relativement élevée (> 10 g/cm3). En effet, les deux principaux métaux précieux utilisés en horlogerie, à savoir l'or et le platine, ont des masses volumiques respectives d'environ 19.3 et 21.5 g/cm3. Ceci a pour conséquence de rendre leurs alliages relativement lourds. L'argent et le palladium sont plus légers (10.5 et 12 g/cm3 respectivement) mais beaucoup moins utilisés dans l'horlogerie.A characteristic common to most precious alloys used in watchmaking is their relatively high density (> 10 g / cm 3 ). Indeed, the two main precious metals used in watchmaking, namely gold and platinum, have respective densities of about 19.3 and 21.5 g / cm 3 . This has the consequence of making their alloys relatively heavy. Silver and palladium are lighter (10.5 and 12 g / cm 3 respectively) but much less used in watchmaking.

D'autre part, l'utilisation de matériaux légers comme le titane et, dans une moindre mesure, l'aluminium, dans des éléments d'habillage horloger est relativement répandue de nos jours. Toutefois, à l'heure actuelle, peu d'alliages peuvent être considérés comme précieux (titrables) et légers à la fois.On the other hand, the use of lightweight materials such as titanium and, to a lesser extent, aluminum, in watchmaking elements is relatively widespread nowadays. However, at present, few alloys can be considered valuable (titratable) and light at a time.

Le document WO 2012/119647 A1 décrit des composites céramique-métal précieux pouvant atteindre des masses volumiques relativement faibles (<8 g/cm3).The document WO 2012/119647 A1 describes ceramic-precious metal composites that can reach relatively low densities (<8 g / cm 3 ).

La réalisation d'alliages de métaux légers et de métaux précieux ne permet généralement pas d'obtenir des matériaux ductiles, et aboutit dans la quasi-totalité des cas à des phases intermétalliques fragiles.The production of alloys of light metals and precious metals generally does not make it possible to obtain ductile materials, and in almost all cases results in fragile intermetallic phases.

Toutefois, une exception existe pour les phases équi-atomiques Ti(Pd/Pt/Au). En effet, ces phases peuvent s'apparenter à la phase équi-atomique TiNi utilisée dans certains alliages à mémoire de forme. De la même manière, les phases équi-atomiques TiPd, TiPt et TiAu possèdent une certaine ductilité et peuvent, sous certaines conditions, présenter des comportements typiques de ceux des alliages à mémoire de forme TiNi. Les alliages équi-atomiques TiPd, TiPt et TiAu sont connus de longue date et ont fait l'objet de plusieurs études visant les alliages à mémoire de forme à haute température.However, an exception exists for the equi-atomic Ti phases (Pd / Pt / Au). Indeed, these phases may be similar to the TiNi equi-atomic phase used in some shape memory alloys. In the same way, the TiPd, TiPt and TiAu equi-atomic phases have a certain ductility and can, under certain conditions, present behaviors typical of TiNi shape memory alloys. The TiPd, TiPt and TiAu equi-atomic alloys have been known for a long time and have been the subject of several studies involving high-temperature shape-memory alloys.

L'effet de l'ajout d'éléments d'addition autres que Ni, Pd, Pt, Au dans ces systèmes a principalement été étudié pour les alliages TiNi. Les recherches portant sur les ajouts ternaires aux alliages TiPd, TiPt et TiAu sont sensiblement plus rares. On sait néanmoins que l'ajout de fer au système TiPd a une influence sur les transformations de phases du système.The effect of adding addition elements other than Ni, Pd, Pt, Au in these systems has mainly been studied for TiNi alloys. Research on ternary additions to TiPd, TiPt and TiAu alloys is significantly less common. It is nevertheless known that the addition of iron to the TiPd system has an influence on the phase transformations of the system.

La majorité de la littérature portant sur les ajouts aux alliages binaires équi-atomiques TiNi, TiPd, TiPt et TiAu se concentre sur la modification des propriétés de mémoire de forme et des propriétés dites super-élastiques de ces alliages (amplitude, température de transition). Cependant, aucune étude ne concerne la problématique de l'utilisation de tels alliages en bijouterie/horlogerie et des contraintes y associées, à savoir la formabilité et le titre (pourcentage de métal précieux).The majority of the literature on additions to TiNi, TiPd, TiPt and TiAu equi-atomic binary alloys focuses on the modification of shape memory properties and so-called superelastic properties of these alloys (amplitude, transition temperature). . However, no study concerns the problem of the use of such alloys in jewelery / watchmaking and the associated constraints, namely the formability and the title (percentage of precious metal).

Les compositions massiques des phases équi-atomiques ductiles des alliages TiPd, TiPt et TiAu sont présentées dans le tableau 1, qui établit la composition des phases équi-atomiques Ti-(Pd, Pt, Au) et la comparaison avec les titres légaux en vigueur en Suisse. Alliage Composition atomique Composition massique approx. Titres légaux en Suisse pour le métal précieux Titre(s) inférieur(s) à la composition équi-atomique TiPd Ti50Pd50 Ti310Pd690 999, 950, 500 500 TiPt Ti50Pt50 Ti197Pt803 999, 900, 850 - TiAu Ti50Au50 Ti196Au804 999, 750, 585, 375 750, 585, 375 The mass compositions of the ductile equi-atomic phases of the TiPd, TiPt and TiAu alloys are presented in Table 1, which establishes the composition of the equi-atomic phases Ti - (Pd, Pt, Au) and the comparison with the legal titles in force. in Swiss. Alloy Atomic composition Mass composition approx. Swiss legal securities for precious metal Title (s) lower than the equi-atomic composition TiPd Ti 50 Pd 50 Ti 310 Pd 690 999, 950, 500 500 TiPt Ti 50 Pt 50 Ti 197 Pt 803 999, 900, 850 - TiAu Ti 50 To 50 Ti 196 To 804 999, 750, 585, 375 750, 585, 375

On remarque que les alliages TiPd et TiAu sont titrables et donc intéressants pour l'horlogerie et la bijouterie comme métaux précieux particulièrement légers.It is noted that TiPd and TiAu alloys are titrable and therefore of interest for watchmaking and jewelery as particularly precious precious metals.

Résumé de l'inventionSummary of the invention

L'invention se propose de réaliser des composants d'habillage d'horlogerie, à la fois précieux pour bénéficier du titre et de la tenue dans le temps et à la corrosion, et plus légers que les alliages connus.The invention proposes to make watchmaking components, both valuable to benefit the title and the resistance over time and corrosion, and lighter than known alloys.

A cet effet, l'invention concerne un composant d'habillage pour pièce d'horlogerie ou de bijouterie, réalisé en alliage précieux léger à base de titane, caractérisé en ce que ledit alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPd1-a-y, avec 0.3<a<0.6, 0<x<0.15, 0.01<y<0.4, et M étant un ou plusieurs parmi un premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.For this purpose, the invention relates to a trim component for a timepiece or jewelery, made of a precious light alloy based on titanium, characterized in that said alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd 1-ay , with 0.3 <a <0.6, 0 <x <0.15, 0.01 <y <0.4, and M being one or more of a first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.

Selon une caractéristique particulière de l'invention, ledit alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPdz, avec 0.44<a<0.55 ; 0<x<0.05 ; 0.07<y<0.28 ; 0.25<z<0.45.According to a particular characteristic of the invention, said alloy obeys the atomic composition Ti ax (Zr, Hf) × M y Pd z , with 0.44 <a <0.55; 0 <x <0.05; 0.07 <y <0.28; 0.25 <z <0.45.

L'invention concerne encore une pièce d'horlogerie ou de bijouterie comportant au moins un tel composant d'habillage.The invention also relates to a timepiece or jewelery comprising at least one such dressing component.

Description sommaire des dessinsBrief description of the drawings

D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description détaillée qui va suivre, en référence aux dessins annexés, où :

  • la figure 1 compare les courbes contrainte-déformation d'alliages testés en compression avec une vitesse de déformation de 0.001 /s :
    • ∘ en trait interrompu Ti50Pd35.5Nb14.5,
    • ∘ en trait continu Ti50Pd32Fe18,
    • ∘ en trait pointillé Ti44.5Pd35Nb11Fe9.5
    • ∘ en trait mixte Ti50Pd50.
  • la figure 2 représente une montre comportant une boîte et un bracelet selon l'invention.
Other features and advantages of the invention will appear on reading the detailed description which follows, with reference to the appended drawings, in which:
  • the figure 1 compares the stress-strain curves of alloys tested in compression with a strain rate of 0.001 / s:
    • ∘ in broken lines Ti 50 Pd 35.5 Nb 14.5 ,
    • ∘ in continuous line Ti 50 Pd 32 Fe 18 ,
    • ∘ dotted line Ti 44.5 Pd 35 Nb 11 Fe 9.5
    • ∘ dotted line Ti 50 Pd 50 .
  • the figure 2 represents a watch comprising a box and a bracelet according to the invention.

Description détaillée des modes de réalisation préférésDetailed Description of the Preferred Embodiments

Toutes les concentrations exprimées dans la description ci-dessous sont atomiques, sauf mention contraire.All concentrations expressed in the description below are atomic unless otherwise stated.

L'invention s'intéresse au remplacement de l'or et du palladium dans des alliages à base de titane.The invention is concerned with the replacement of gold and palladium in titanium-based alloys.

L'invention concerne un composant d'habillage 1 d'horlogerie ou de bijouterie (incluant la joaillerie) en alliage précieux léger à base de titane, et toute pièce d'horlogerie ou de bijouterie comportant un tel composant.The invention relates to a dressing component 1 of watches or jewelery (including jewelery) precious alloy light titanium base, and any timepiece or jewelry including such a component.

L'utilisation d'alliages, tels que décrits plus haut dans le tableau 1, qui sont surchargés en métal précieux par rapport aux titres auxquels ils peuvent être poinçonnés, engendrent un surcoût inutile. Afin de résoudre ce problème, des substituts avantageux peuvent convenir pour la surcharge de métal précieux, et notamment les métaux d'un deuxième groupe comportant : Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.The use of alloys, as described above in Table 1, which are overloaded with precious metal with respect to the titles to which they can be punched, generates an unnecessary extra cost. In order to solve this problem, advantageous substitutes may be suitable for the overloading of precious metal, and in particular the metals of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo , Ta, W.

Ces éléments peuvent être introduits en grande quantité (>10% atomique) dans les alliages TiPd et TiAu en remplacement du palladium et de l'or, respectivement. Par exemple, la ductilité en compression des alliages Ti50Pd35.5Nb14.5, Ti50Pd32Fe18 et Ti44.5Pd35Nb11Fe9.5 (% at.) n'est pas significativement différente de celle d'un alliage binaire équi-atomique TiPd, tel que visible sur la figure 1, qui compare les courbes contrainte-déformation d'alliages Ti50Pd35.5Nb14.5, Ti50Pd32Fe18, Ti44.5Pd35Nb11Fe9.5 et Ti50Pd50, testés en compression avec une vitesse de déformation de 0.001 /s.These elements can be introduced in large quantities (> 10 atomic%) in the TiPd and TiAu alloys instead of palladium and gold, respectively. For example, the compressive ductility of Ti 50 Pd 35.5 Nb 14.5 , Ti 50 Pd 32 Fe 18 and Ti 44.5 Pd 35 Nb 11 Fe 9.5 alloys (% at.) Is not significantly different from that of an equivalent binary alloy. -atomic TiPd, as visible on the figure 1 , which compares the stress-strain curves of alloys Ti 50 Pd 35.5 Nb 14.5 , Ti 50 Pd 32 Fe 18 , Ti 44.5 Pd 35 Nb 11 Fe 9.5 and Ti 50 Pd 50 , tested in compression with a strain rate of 0.001 / s.

Les éléments d'un troisième groupe comportant : Cr, Mn, Cu, Zn et Ag, peuvent être introduits en quantité limitée (<10% at.) dans les alliages TiPd et TiAu en remplacement du palladium et de l'or, respectivement.The elements of a third group comprising: Cr, Mn, Cu, Zn and Ag can be introduced in a limited amount (<10 at%) in the TiPd and TiAu alloys instead of palladium and gold, respectively.

Finalement, les éléments d'un quatrième groupe comportant : Al, Si, Ge, Sn, Sb et In, peuvent être introduits en faible quantité (<4% at.) dans les alliages TiPd et TiAu en remplacement du titane ou du palladium et de l'or, respectivement.Finally, the elements of a fourth group comprising: Al, Si, Ge, Sn, Sb and In can be introduced in small quantities (<4 at%) in TiPd and TiAu alloys in place of titanium or palladium and gold, respectively.

Idéalement, pour des applications en contact avec le corps humain, les matériaux de substitution ne doivent pas générer de risques pour la santé. Pour réduire efficacement le surcoût dû à la présence de métal précieux, les matériaux de substitution de ce dernier ne doivent pas être précieux. Finalement, afin de ne pas trop alourdir l'alliage, les matériaux de substitution, idéalement, ne sont pas plus lourds que le métal substitué.Ideally, for applications in contact with the human body, substitute materials should not generate health risks. To effectively reduce the extra cost due to the presence of precious metal, the substitute materials of the latter must not be valuable. Finally, in order not to overload the alloy, the substitute materials, ideally, are not heavier than the substituted metal.

Une mise en oeuvre particulièrement avantageuse de l'invention concerne la substitution d'une partie du palladium dans un alliage TiPd.A particularly advantageous embodiment of the invention relates to the substitution of a part of the palladium in a TiPd alloy.

L'invention concerne alors un alliage ductile basé sur l'intermétallique équi-atomique Ti-Pd, dans lequel le surplus de palladium par rapport au titre massique de Pd500 est partiellement ou totalement remplacé par un élément non précieux, de telle sorte que le titane représente toujours 50% atomique de l'alliage final. Un tel alliage présente une ductilité suffisante pour offrir une formabilité similaire à celle d'alliages de titane conventionnels.The invention thus relates to a ductile alloy based on the Ti-Pd equi-atomic intermetallic, in which the excess of palladium relative to the mass content of Pd500 is partially or totally replaced by a non-precious element, so that the titanium still represents 50 atomic% of the final alloy. Such an alloy has sufficient ductility to provide a formability similar to that of conventional titanium alloys.

Il s'agit donc de réduire le surtitrage, par une substitution d'une partie du palladium, sans impacter défavorablement la ductilité.It is therefore a question of reducing the surtitling, by a substitution of a part of the palladium, without adversely impacting the ductility.

Les alliages ternaires TiPdFe et TiPdNb permettent d'atteindre le titre souhaité. Tout particulièrement, les alliages TiPdNb ne présentent pas d'effet parasite de mémoire de forme, ce qui est avantageux.The TiPdFe and TiPdNb ternary alloys make it possible to attain the desired title. In particular, TiPdNb alloys do not exhibit a parasitic shape memory effect, which is advantageous.

La composition de l'alliage peut être formulée selon une des compositions suivantes, où toutes les fractions sont atomiques :The composition of the alloy may be formulated according to one of the following compositions, in which all the fractions are atomic:

Premièrefirst composition :composition:

On remplace une partie du titane par une même quantité atomique de zirconium ou de hafnium, ces trois éléments ayant des propriétés chimiques très proches et étant facilement substituables les uns par les autres :

         Tia-x(Zr,Hf)xMyPd1-a-y

         0.3<a<0.6 ; 0<x<0.15 ; 0.01<y<0.4

M = un ou plusieurs parmi un premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.
a définit le décalage par rapport à la composition équi-atomique.
x définit le degré de remplacement du titane par Zr et Hf.
y définit la fraction d'élément de substitution.Part of the titanium is replaced by the same atomic quantity of zirconium or hafnium, these three elements having very similar chemical properties and being easily substitutable with each other:

Ti ax (Zr, Hf) x M y Pd 1-ay

0.3 <a <0.6; 0 <x <0.15; 0.01 <y <0.4

M = one or more of a first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, If, Ge, Sn, Sb, In.
a defines the offset with respect to the equi-atomic composition.
x defines the degree of replacement of titanium by Zr and Hf.
defines the fraction of substitution element.

Deuxième composition : Second composition :



        Tia-x(Zr,Hf)xMyPd1-a-y

         0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4

Ti ax ( Zr, Hf) x M y Pd 1-ay

0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4

Restriction du taux de Zr, Hf, par rapport à la première compositionRestriction of the Zr, Hf rate, compared to the first composition

Troisième composition : Third composition :



        Tia-x(Zr,Hf)xMyPdz

         0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4 ; 0.2<z<0.55

Ti ax (Zr, Hf) x M y Pd z

0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4; 0.2 <z <0.55

Quatrième composition : Fourth composition :



        Tia-x(Zr,Hf)xMyPdz

0.44<a<0.55 ; 0<x<0.05 ; 0.07<y<0.28 ; 0.25<z<0.45

Ti ax (Zr, Hf) x M y Pd z

0.44 <a <0.55; 0 <x <0.05; 0.07 <y <0.28; 0.25 <z <0.45

Parmi la quatrième composition, les compositions particulières qui suivent conviennent particulièrement bien : Ti0.5Pd0.52Fe0.18 a = 0.5, x = 0, y = 0.1 8, z = 0.32 Ti0.5Pd0.354Nb0.146 a = 0.5, x = 0, y = 0.146, z = 0.354 Ti0.5Pd0.404Au0.09 a = 0.5, x = 0, y = 0.096, z = 0.404 Ti0.5Pd0.323Co0.177 a = 0.5, x = 0, y = 0.177, z = 0.323 Ti0.5Pd0.32Fe0.17Cr0.01 a = 0.5, x = 0, y = 0.1 8, z = 0.32 Ti0.5Pd0.32Fe0.17Cu0.01 a = 0.5, x = 0, y = 0.1 8, z = 0.32 Ti0.49Zr0.01Pd0.323Fe0.177 a = 0.5, x = 0.01, y = 0.177, z = 0.323 Ti0.49Pd0.317Fe0.173Al0.02 a = 0.49, x = 0, y = 0.193, z = 0.317 Ti0.445Pd0.35Nb0.11Fe0.095 a = 0.445, x = 0, y = 0.205, z = 0.35 Among the fourth composition, the particular compositions which follow are particularly suitable: Ti 0.5 Pd 0.52 Fe 0.18 a = 0.5, x = 0, y = 0.18, z = 0.32 Ti 0.5 Pd 0.354 Nb 0.146 a = 0.5, x = 0, y = 0.146, z = 0.354 Ti 0.5 Pd 0.404 At 0.09 a = 0.5, x = 0, y = 0.096, z = 0.404 Ti 0.5 Pd 0.323 Co 0.177 a = 0.5, x = 0, y = 0.177, z = 0.323 Ti 0.5 Pd 0.32 Fe 0.17 Cr 0.01 a = 0.5, x = 0, y = 0.18, z = 0.32 Ti 0.5 Pd 0.32 Fe 0.17 Cu 0.01 a = 0.5, x = 0, y = 0.18, z = 0.32 Ti 0.49 Zr 0.01 Pd 0.323 Fe 0.177 a = 0.5, x = 0.01, y = 0.177, z = 0.323 Ti 0.49 Pd 0.317 Fe 0.173 Al 0.02 a = 0.49, x = 0, y = 0.193, z = 0.317 Ti 0.445 Pd 0.35 Nb 0.11 Fe 0.095 a = 0.445, x = 0, y = 0.205, z = 0.35

CinquièmeFifth composition:composition:

Composition selon la quatrième composition, et pour laquelle M comporte un ou plusieurs éléments pris parmi un cinquième groupe comportant : Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.Composition according to the fourth composition, and for which M comprises one or more elements taken from a fifth group comprising: Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.

En substitution totale du palladium, le chrome et le cuivre rendent l'alliage fragile. Le manganèse, le zinc, l'argent, l'aluminium, le silicium, le germanium, l'indium, l'étain et le molybdène peuvent avoir, dans certaines conditions, un effet similaire. Leur teneur doit donc être limitée, et le fer et le niobium sont préférés pour constituer les éléments de substitution majoritaires.In complete substitution of palladium, chromium and copper make the alloy fragile. Manganese, zinc, silver, aluminum, silicon, germanium, indium, tin and molybdenum may, under certain conditions, have a similar effect. Their content must therefore be limited, and iron and niobium are preferred to constitute the majority substitution elements.

SixièmeSixth composition :composition:

Composition selon la cinquième composition, et pour laquelle M comporte Fe et/ou Nb comme éléments majoritaires.Composition according to the fifth composition, and for which M comprises Fe and / or Nb as majority elements.

SeptièmeSeventh composition :composition:

Composition selon la sixième composition, et contenant 50% en masse de palladium.Composition according to the sixth composition, and containing 50% by weight of palladium.

HuitièmeEighth composition :composition:

Alliages TiPdFeCrTiPdFeCr alloys AtomiqueAtomic Massiquemass TiTi PdPd FeFe CrCr TotalTotal TiTi PdPd FeFe CrCr TotalTotal 49.749.7 3232 15.315.3 33 100100 35.0135.01 50.1250.12 12.5712.57 2.32.3 100100 49.749.7 3232 12.312.3 66 100100 35.0735.07 50.250.2 10.1310.13 4.64.6 100100 49.749.7 31.931.9 10.410.4 88 100100 35.1435.14 50.1450.14 8.588.58 6.146.14 100100

Plus particulièrement, la composition atomique Ti49.7Pd32Fe15.3Cr3 présente des caractéristiques intéressantes : effet mémoire faible, quantité de deuxième phase faible, et propriétés mécaniques pas trop élevées.More particularly, the Ti49.7Pd32Fe15.3Cr3 atomic composition has interesting characteristics: low memory effect, low second phase quantity, and not too high mechanical properties.

NeuvièmeNinth composition :composition:

Alliages TiPdNbTiPdNb alloys AtomiqueAtomic Massiquemass TiTi PdPd NbNb TotalTotal TiTi PdPd NbNb TotalTotal 49.749.7 37.837.8 12.512.5 100100 31.4631.46 53.1853.18 15.3615.36 100100 49.749.7 39.839.8 10.510.5 100100 31.3431.34 55.855.8 12.8612.86 100100

Les compositions de cette neuvième composition contenant atomiquement 12.5 et 10.5 % de niobium présentent un effet mémoire de forme alors que la composition Ti50Pd35.5Nb14.5 de la figure 1 contenant 14.5% de niobium ne présente pas d'effet de cette nature. Cette composition à 14.5% de niobium permet de s'affranchir de ces effets grâce à sa nature biphasée.The compositions of this ninth composition containing atomically 12.5 and 10.5% of niobium exhibit a shape memory effect while the composition Ti 50 Pd 35.5 Nb 14.5 of the figure 1 containing 14.5% niobium has no effect of this kind. This 14.5% niobium composition makes it possible to overcome these effects thanks to its two-phase nature.

De façon générale, de faibles écarts de compositions, notamment concernant celle du titane, de l'ordre de 0,3% du total, ne changent pas foncièrement les propriétés de ces différentes compositions, et n'altèrent pas leur aptitude au remplacement des alliages classiques.In general, small variations in compositions, in particular as regards titanium, of the order of 0.3% of the total, do not fundamentally change the properties of these various compositions, and do not affect their ability to replace alloys. classics.

L'invention concerne ainsi un composant d'habillage pour pièce d'horlogerie ou de bijouterie, réalisé en alliage précieux léger à base de titane. Selon la première composition exposée plus haut, la composition de cet alliage obéit à la composition atomique :

         Tia-x(Zr,Hf)xMyPd1-a-y,

avec 0.3<a<0.6, 0<x<0.15, 0.01<y<0.4,
et M étant un ou plusieurs parmi un premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.The invention thus relates to a cladding component for a timepiece or jewelery, made of a precious precious alloy based on titanium. According to the first composition described above, the composition of this alloy obeys the atomic composition:

Ti ax (Zr, Hf) x M y Pd 1-ay ,

with 0.3 <a <0.6, 0 <x <0.15, 0.01 <y <0.4,
and M being one or more of a first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al , Si, Ge, Sn, Sb, In.

Plus particulièrement, cet alliage comporte entre 15 et 60 % atomique de titane, entre 0 et 69% atomique de palladium, entre 1 et 40% atomique d'or, et le complément à 100% atomique comporte un total compris entre 0 et 15% atomique de zirconium et hafnium, et un ou plusieurs composants pris parmi un sous-groupe du premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.More particularly, this alloy comprises between 15 and 60 atomic% of titanium, between 0 and 69 atomic% of palladium, between 1 and 40 atomic% of gold, and the complement at 100 atomic% comprises a total included between 0 and 15% atomic composition of zirconium and hafnium, and one or more components selected from a subgroup of the first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Pt, Cr, Mn , Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.

Dans une alternative, l'alliage comporte en % atomique davantage de palladium que d'or.In an alternative, the alloy comprises in atomic% more palladium than gold.

Plus particulièrement, l'alliage comporte entre 30% et 60% atomique de titane, et le reste du dit alliage comporte une majorité de palladium, et, en quantité supérieure à 10% atomique du total de l'alliage, au moins un métal d'un deuxième groupe comportant : Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.More particularly, the alloy comprises between 30% and 60% by weight of titanium, and the remainder of said alloy comprises a majority of palladium, and, in an amount greater than 10% by weight of the total of the alloy, at least one metal of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.

Dans une autre alternative, l'alliage comporte entre 30% et 60% atomique de titane, et le reste de cet alliage comporte une majorité d'or, et, en quantité supérieure à 10% atomique du total de l'alliage, au moins un métal d'un deuxième groupe comportant : Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.In another alternative, the alloy comprises between 30% and 60% by weight of titanium, and the remainder of this alloy comprises a majority of gold, and, in an amount greater than 10% by weight of the total of the alloy, at least a metal of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.

Dans une réalisation particulière, l'alliage comporte au moins un métal d'un troisième groupe comportant : Cr, Mn, Cu, Zn et Ag, la quantité globale des métaux dudit troisième groupe est inférieure à 10% atomique du total de l'alliage.In a particular embodiment, the alloy comprises at least one metal of a third group comprising: Cr, Mn, Cu, Zn and Ag, the total quantity of the metals of said third group is less than 10 atomic% of the total of the alloy .

Dans une autre réalisation particulière, l'alliage comporte au moins un métal d'un quatrième groupe comportant : Al, Si, Ge, Sn, Sb et In, la quantité globale des métaux du quatrième groupe est inférieure à 4% atomique du total de l'alliage.In another particular embodiment, the alloy comprises at least one metal of a fourth group comprising: Al, Si, Ge, Sn, Sb and In, the overall quantity of the metals of the fourth group is less than 4 atomic% of the total of the alloy.

Dans une réalisation particulière, l'alliage comporte entre 49.0 et 51.0% atomique de titane.In a particular embodiment, the alloy has between 49.0 and 51.0 at% titanium.

Dans une autre réalisation particulière, le total en % atomique du titane, du zirconium, et du hafnium, est compris entre 49.0 et 51.0 % atomique.In another particular embodiment, the total atomic% of titanium, zirconium and hafnium is between 49.0 and 51.0 at%.

Selon la deuxième composition exposée plus haut, l'alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPd1-a-y, avec 0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4.According to the second composition described above, the alloy obeys the atomic composition Ti ax (Zr, Hf) × M y Pd 1-ay , with 0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4.

Selon la troisième composition exposée plus haut, l'alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPdz, avec 0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4 ; 0.2<z<0.55.According to the third composition described above, the alloy obeys the atomic composition Ti ax (Zr, Hf) × M y Pd z , with 0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4; 0.2 <z <0.55.

Selon la quatrième composition exposée plus haut, l'alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPdz, avec 0.44<a<0.55 ; 0<x<0.05 ; 0.07<y<0.28 ; 0.25<z<0.45.According to the fourth composition described above, the alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd z , with 0.44 <a <0.55; 0 <x <0.05; 0.07 <y <0.28; 0.25 <z <0.45.

Plus particulièrement, selon des variantes de cette quatrième composition :

  • l'alliage obéit à la composition atomique TirPdsFet, avec r compris entre 49.5 et 50.5 % atomique, s compris entre 31.5 et 32.5% atomique, t compris entre 17.5 et 18.5% atomique, avec r+s+t=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.32Fe0.18.
  • l'alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.5 et 50.5% atomique, s compris entre 34.9 et 35.9% atomique, u compris entre 14.1 et 15.1% atomique, avec r+s+u=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.354Nb0.146.
  • l'alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.2 et 50.2% atomique, s compris entre 37.3 et 40.3% atomique, u compris entre 10.0 et 13.0% atomique, avec r+s+u=100, avec des variantes selon la neuvième composition exposée ci-dessus :
    • o l'alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.2 et 50.2% atomique, s compris entre 37.3 et 38.3% atomique, u compris entre 12.0 et 13.0% atomique, avec r+s+u=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.378Nb0.125
    • o l'alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.2 et 50.2% atomique, s compris entre 39.3 et 40.3% atomique, u compris entre 10.0 et 11.0% atomique, avec r+s+u=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.398Nb0.105
  • l'alliage obéit à la composition atomique TirPdsAuv, avec r compris entre 49.5 et 50.5% atomique, s compris entre 39.9 et 40.9% atomique, v compris entre 8.5 et 9.5% atomique, avec r+s+v=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.404Au0.09.
  • l'alliage obéit à la composition atomique TirPdsCow, avec r compris entre 49.5 et 50.5% atomique, s compris entre 31.8 et 32.8% atomique, w compris entre 17.2 et 18.2% atomique, avec r+s+w=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.323Co0.177.
  • l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.5 et 50.5% atomique, s compris entre 31.5 et 32.5% atomique, c compris entre 16.5 et 17.5% atomique, d compris entre 0.5 et 1.5% atomique, avec r+s+c+d=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.32Fe0.17Cr0.01.
  • l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 9.9 et 15.8% atomique, d compris entre 2.5 et 8.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100. Selon des variantes décrites selon la huitième composition exposée ci-dessus:
    • o l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 14.8 et 15.8% atomique, d compris entre 2.5 et 3.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.32Fe0.153Cr0.03. Selon d'autres variantes :
    • o l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 11.8 et 12.8% atomique, d compris entre 5.5 et 6.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.32Fe0.123Cr0.06
    • o l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 9.9 et 10.9% atomique, d compris entre 7.7 et 8.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.319Fe0.104Cr0.08
  • l'alliage obéit à la composition atomique TirPdsFeeCuf, avec r compris entre 49.5 et 50.5% atomique, s compris entre 31.5 et 32.5% atomique, e compris entre 16.5 et 17.5% atomique, f compris entre 0.5 et 1.5% atomique, avec r+s+e+f=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.32Fe0.17Cu0.01.
  • l'alliage obéit à la composition atomique TirPdsFegZrh, avec r compris entre 48.5 et 49.5% atomique, s compris entre 31.8 et 32.8% atomique, g compris entre 17.2 et 18.2% atomique, h compris entre 0.5 et 1.5% atomique, avec r+s+g+h=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.49Zr0.01 Pd0.323Fe0.177.
  • l'alliage obéit à la composition atomique TirPdsFejAlk, avec r compris entre 48.5 et 49.5% atomique, s compris entre 31.2 et 32.2% atomique, j compris entre 16.8 et 17.8% atomique, k compris entre 1.5 et 2.5% atomique, avec r+s+j+k=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.49Pd0.317Fe0.173Al0.02.
    • l'alliage obéit à la composition atomique TirPdsFemNbn, avec r compris entre 44.0 et 45.0 % atomique, s compris entre 34.5 et 35.5% atomique, m compris entre 9.0 et 10.0% atomique, n compris entre 10.5 et 11.5% atomique, avec r+s+m+n=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.445Pd0.35Nb0.11Fe0.095.
More particularly, according to variants of this fourth composition:
  • the alloy obeys the atomic composition Ti r Pd s Fe t , with r ranging between 49.5 and 50.5 atomic%, s between 31.5 and 32.5 atomic%, t between 17.5 and 18.5 atomic%, with r + s + t = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.32 Fe 0.18 .
  • the alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.5 and 50.5 atomic%, s between 34.9 and 35.9 atomic%, u between 14.1 and 15.1 atomic%, with r + s + u = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.354 Nb 0.146 .
  • the alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.2 and 50.2 at%, s between 37.3 and 40.3 at%, u between 10.0 and 13.0 at%, with r + s + u = 100, with variants according to the ninth composition set forth above:
    • the alloy obeys the atomic composition Ti r Pd s Nb u , with r ranging between 49.2 and 50.2 at%, s between 37.3 and 38.3 at%, u being between 12.0 and 13.0 at%, with r + s + u = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.378 Nb 0.125
    • the alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.2 and 50.2 at%, s between 39.3 and 40.3 at%, u between 10.0 and 11.0 at%, with r + s + u = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.398 Nb 0.105
  • the alloy obeys the atomic composition Ti r Pd s Au v , with r between 49.5 and 50.5 atomic%, s between 39.9 and 40.9 atomic%, v between 8.5 and 9.5 atomic%, with r + s + v = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.404 Au 0.09 .
  • the alloy obeys the atomic composition Ti r Pd s Co w , with r between 49.5 and 50.5 atomic%, s between 31.8 and 32.8 atomic%, w between 17.2 and 18.2 atomic%, with r + s + w = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.323 Co 0.177 .
  • the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r ranging between 49.5 and 50.5 at%, s between 31.5 and 32.5 at%, c between 16.5 and 17.5 at%, d between 0.5 and 1.5 atomic%, with r + s + c + d = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.32 Fe 0.17 Cr 0.01 .
  • the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r ranging between 49.2 and 50.2 at%, s between 31.4 and 32.5 at%, including between 9.9 and 15.8 at%, d between 2.5 and 8.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. According to variants described according to the eighth composition exposed above:
    • the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r ranging from 49.2 to 50.2 at%, s ranging from 31.4 to 32.5 at%, ranging from 14.8 to 15.8 at%, d ranging from 2.5 and 3.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.32 Fe 0.153 Cr 0.03 . According to other variants:
    • the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r ranging from 49.2 to 50.2 at%, s ranging from 31.4 to 32.5 atomic%, ranging from 11.8 to 12.8 atomic%, ranging from 5.5 and 6.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.32 Fe 0.123 Cr 0.06
    • the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r ranging from 49.2 to 50.2 at%, s ranging from 31.4 to 32.5 at%, ranging from 9.9 to 10.9 atomic%, ranging from 7.7 and 8.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.319 Fe 0.104 Cr 0.08
  • the alloy obeys the atomic composition Ti r Pd s Fe e Cu f , with r between 49.5 and 50.5 atomic%, s between 31.5 and 32.5 atomic%, e between 16.5 and 17.5 atomic%, f between 0.5 and 1.5 atomic%, with r + s + e + f = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.32 Fe 0.17 Cu 0.01 .
  • the alloy obeys the atomic composition Ti r Pd s Fe g Zr h , with r ranging from 48.5 to 49.5 at%, s ranging from 31.8 to 32.8 atomic%, ranging from 17.2 to 18.2 at%, h being between 0.5 and 1.5 atomic%, with r + s + g + h = 100. More particularly, the alloy obeys the atomic composition Ti 0.49 Zr 0.01 Pd 0.323 Fe 0.177 .
  • the alloy obeys the atomic composition Ti r Pd s Fe j Al k , with r ranging between 48.5 and 49.5 at%, s between 31.2 and 32.2 at%, including between 16.8 and 17.8 at%, k between 1.5 and 2.5 atomic%, with r + s + j + k = 100. More particularly, the alloy obeys the atomic composition Ti 0.49 Pd 0.317 Fe 0.173 Al 0.02 .
    • the alloy obeys the atomic composition Ti r Pd s Fe m Nb n , with r ranging between 44.0 and 45.0 at%, s between 34.5 and 35.5 atomic%, m between 9.0 and 10.0 atomic%, n between 10.5 and 11.5 atomic%, with r + s + m + n = 100. More particularly, the alloy obeys the atomic composition Ti 0.445 Pd 0.35 Nb 0.11 Fe 0.095 .

Selon la cinquième composition exposée ci-dessus, M comporte un ou plusieurs éléments pris parmi un cinquième groupe comportant : Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.According to the fifth composition described above, M comprises one or more elements taken from a fifth group comprising: Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.

Selon la sixième composition exposée ci-dessus, M comporte Fe et/ou Nb comme éléments majoritaires.According to the sixth composition described above, M comprises Fe and / or Nb as majority elements.

Selon la septième composition exposée ci-dessus, l'alliage comporte 50% en masse de palladium.According to the seventh composition described above, the alloy comprises 50% by weight of palladium.

L'invention concerne encore une pièce d'horlogerie 10 ou de bijouterie, notamment une montre, comportant au moins un tel composant d'habillage 1.The invention also relates to a timepiece 10 or jewelery, including a watch, comprising at least one such dressing component 1.

En résumé, pour l'ensemble des compositions selon l'invention, les différents alliages sélectionnés ci-dessus sont ductiles, et permettent donc une mise en forme par les procédés habituels de déformation.In summary, for all the compositions according to the invention, the various alloys selected above are ductile, and therefore allow shaping by the usual methods of deformation.

Ces alliages sont encore :

  • précieux, au sens légal du terme (aloi) ;
  • particulièrement légers en comparaison avec la majorité des alliages précieux, au sens légal du terme ;
  • sans danger pour le corps humain ;
  • très résistants à la corrosion.
These alloys are still:
  • valuable, in the legal sense of the term (aloi);
  • particularly light in comparison with the majority of precious alloys, in the legal sense of the term;
  • safe for the human body
  • very resistant to corrosion.

La réalisation de composants d'habillage horloger en l'un des alliages cités plus haut bénéficie de l'optimisation de la composition de l'alliage selon différents angles :

  • ajout d'éléments abaissant le point de fusion afin de faciliter la mise en oeuvre ;
  • modification de la teneur en élément de remplacement du métal précieux afin de modifier les propriétés mécaniques de l'alliage ;
  • diverses modifications légères visant à obtenir des alliages à durcissement structural.
The production of clockwork components in one of the alloys mentioned above benefits from the optimization of the composition of the alloy from different angles:
  • addition of elements lowering the melting point to facilitate implementation;
  • modifying the content of the replacement element of the precious metal in order to modify the mechanical properties of the alloy;
  • various light modifications to obtain alloys with structural hardening.

La sélection des alliages avec composants de substitution selon l'invention permet, encore, de supprimer l'effet mémoire de forme observé dans la plupart des alliages de base décrits. Par exemple, l'alliage Ti0.5Pd0.354Nb0.146 présente un effet mémoire de forme quasi nul.The selection of alloys with substitution components according to the invention makes it possible, again, to eliminate the shape memory effect observed in most of the base alloys described. For example, the alloy Ti 0.5 Pd 0.354 Nb 0.146 has an almost zero shape memory effect.

L'invention autorise de nombreuses applications, et, notamment et de façon non limitative :

  • éléments d'habillage: carrures, fonds, lunettes de montres, et éléments d'habillage externe (poussoirs, fermoirs, bracelets) ;
  • bijoux, composants de mouvement et d'habillage interne de montres.
The invention authorizes many applications, and in particular and without limitation:
  • trim elements: middle, back, watch glasses, and external trim elements (pushers, clasps, bracelets);
  • jewelry, movement components and internal cladding of watches.

Claims (32)

Composant d'habillage (1) pour pièce d'horlogerie ou de bijouterie, réalisé en alliage précieux léger à base de titane, caractérisé en ce que ledit alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPd1-a-y, avec 0.3<a<0.6, 0<x<0.15, 0.01<y<0.4, et M étant un ou plusieurs parmi un premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.Component covering (1) for a timepiece or a jewelery piece, made of a precious precious alloy based on titanium, characterized in that said alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd 1- ay , with 0.3 <a <0.6, 0 <x <0.15, 0.01 <y <0.4, and M being one or more of a first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In. Composant d'habillage (1) selon la revendication 1, caractérisé en ce que ledit alliage comporte entre 15 et 60 % atomique de titane, entre 0 et 69% atomique de palladium, entre 1 et 40% atomique d'or, et le complément à 100% atomique comportant un total compris entre 0 et 15% atomique de zirconium et hafnium, et un ou plusieurs composants pris parmi un sous-groupe du premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.Cladding component (1) according to claim 1, characterized in that said alloy comprises between 15 and 60 atomic% of titanium, between 0 and 69 atomic% of palladium, between 1 and 40 atomic% of gold, and the complement at 100% atomic having a total of between 0 and 15 atomic% zirconium and hafnium, and one or more components selected from a subgroup of the first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In. Composant d'habillage (1) selon la revendication 1 ou 2, caractérisé en ce que ledit alliage comporte en % atomique davantage de palladium que d'or.Cladding component (1) according to claim 1 or 2, characterized in that said alloy comprises in atomic% more palladium than gold. Composant d'habillage (1) selon la revendication 3, caractérisé en ce que ledit alliage comporte entre 30% et 60% atomique de titane, et en ce que le reste du dit alliage comporte une majorité de palladium, et, en quantité supérieure à 10% atomique du total dudit alliage, au moins un métal d'un deuxième groupe comportant : Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.Cladding component (1) according to claim 3, characterized in that said alloy comprises between 30% and 60% by weight of titanium, and in that the remainder of said alloy comprises a majority of palladium, and, in an amount greater than 10 atomic% of the total of said alloy, at least one metal of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W. Composant d'habillage (1) selon la revendication 2, caractérisé en ce que ledit alliage comporte entre 30% et 60% atomique de titane, et en ce que le reste du dit alliage comporte une majorité d'or, et, en quantité supérieure à 10% atomique du total dudit alliage, au moins un métal d'un deuxième groupe comportant : Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.Cladding component (1) according to claim 2, characterized in that said alloy comprises between 30% and 60% by weight of titanium, and in that the remainder of said alloy comprises a majority of gold, and in greater quantity at 10 atomic% of the total of said alloy, at least one metal of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W. Composant d'habillage (1) selon la revendication 4 ou 5, caractérisé en ce que ledit alliage comporte au moins un métal d'un troisième groupe comportant : Cr, Mn, Cu, Zn et Ag, la quantité globale desdits métaux dudit troisième groupe étant inférieure à 10% atomique du total dudit alliage.Cladding component (1) according to claim 4 or 5, characterized in that said alloy comprises at least one metal of a third group comprising: Cr, Mn, Cu, Zn and Ag, the total quantity of said metals of said third group being less than 10 atomic% of the total of said alloy. Composant d'habillage (1) selon l'une des revendications 4 à 6, caractérisé en ce que ledit alliage comporte au moins un métal d'un quatrième groupe comportant : Al, Si, Ge, Sn, Sb et In, la quantité globale desdits métaux dudit quatrième groupe étant inférieure à 4% atomique du total dudit alliage.Cladding component (1) according to one of claims 4 to 6, characterized in that said alloy comprises at least one metal of a fourth group comprising: Al, Si, Ge, Sn, Sb and In, the overall quantity said metals of said fourth group being less than 4 atomic% of the total of said alloy. Composant d'habillage (1) selon l'une des revendications 1 à 7, caractérisé en ce que ledit alliage comporte entre 49.0 et 51.0% atomique de titane.Cladding component (1) according to one of claims 1 to 7, characterized in that said alloy has between 49.0 and 51.0 at% titanium. Composant d'habillage (1) selon l'une des revendications 1 à 7, caractérisé en ce que le total en % atomique du titane, du zirconium, et du hafnium, est compris entre 49.0 et 51.0 % atomique.Cladding component (1) according to one of Claims 1 to 7, characterized in that the total atomic% of titanium, zirconium and hafnium is between 49.0 and 51.0 at%. Composant d'habillage (1) selon la revendication 1, caractérisé en ce que ledit alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPd1-a-y, avec 0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4Cladding component (1) according to claim 1, characterized in that said alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd 1-ay , with 0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4 Composant d'habillage (1) selon la revendication 1, caractérisé en ce que ledit alliage obéit à la composition atomique Tia-xZr,Hf)xMyPdz, avec 0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4 ; 0.2<z<0.55Cladding component (1) according to claim 1, characterized in that said alloy obeys the atomic composition Ti ax Zr, Hf) x M y Pd z , with 0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4; 0.2 <z <0.55 Composant d'habillage (1) selon la revendication 1, caractérisé en ce que ledit alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPdz, avec 0.44<a<0.55 ; 0<x<0.05 ; 0.07<y<0.28 ; 0.25<z<0.45.Cladding component (1) according to claim 1, characterized in that said alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd z , with 0.44 <a <0.55; 0 <x <0.05; 0.07 <y <0.28; 0.25 <z <0.45. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFet, avec r compris entre 49.5 et 50.5 % atomique, s compris entre 31.5 et 32.5% atomique, t compris entre 17.5 et 18.5% atomique, avec r+s+t=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe t , with r between 49.5 and 50.5 atomic%, s between 31.5 and 32.5 at%, t between 17.5 and 18.5 atomic%, with r + s + t = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.5 et 50.5% atomique, s compris entre 34.9 et 35.9% atomique, u compris entre 14.1 et 15.1% atomique, avec r+s+u=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.5 and 50.5 atomic%, s between 34.9 and 35.9 at%, u between 14.1 and 15.1 at%, with r + s + u = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.2 et 50.2% atomique, s compris entre 37.3 et 40.3% atomique, u compris entre 10.0 et 13.0% atomique, avec r+s+u=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.2 and 50.2 at%, s between 37.3 and 40.3 at%, u between 10.0 and 13.0 at%, with r + s + u = 100. Composant d'habillage (1) selon la revendication 15, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.2 et 50.2% atomique, s compris entre 37.3 et 38.3% atomique, u compris entre 12.0 et 13.0% atomique, avec r+s+u=100.Cladding component (1) according to claim 15, characterized in that said alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.2 and 50.2 at%, s between 37.3 and 38.3 at%, u between 12.0 and 13.0 at%, with r + s + u = 100. Composant d'habillage (1) selon la revendication 15, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.2 et 50.2% atomique, s compris entre 39.3 et 40.3% atomique, u compris entre 10.0 et 11.0% atomique, avec r+s+u=100.Cladding component (1) according to claim 15, characterized in that said alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.2 and 50.2 at%, s between 39.3 and 40.3 at%, u between 10.0 and 11.0 at%, with r + s + u = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsAuv, avec r compris entre 49.5 et50.5% atomique, s compris entre 39.9 et 40.9% atomique, v compris entre 8.5 et 9.5% atomique, avec r+s+v=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Au v , with r between 49.5 and 50.5 atomic%, s between 39.9 and 40.9 at%, v between 8.5 and 9.5 atomic%, with r + s + v = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsCow, avec r compris entre 49.5 et 50.5% atomique, s compris entre 31.8 et 32.8% atomique, w compris entre 17.2 et 18.2% atomique, avec r+s+w=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Co w , with r between 49.5 and 50.5 atomic%, s between 31.8 and 32.8 at%, w between 17.2 and 18.2 at%, with r + s + w = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.5 et 50.5% atomique, s compris entre 31.5 et 32.5% atomique, c compris entre 16.5 et 17.5% atomique, d compris entre 0.5 et 1.5% atomique, avec r+s+c+d=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r between 49.5 and 50.5 at%, s between 31.5 and 32.5 at% , between 16.5 and 17.5 at%, d between 0.5 and 1.5 atomic%, with r + s + c + d = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 9.9 et 15.8% atomique, d compris entre 2.5 et 8.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r ranging between 49.2 and 50.2 at%, s between 31.4 and 32.5 at% , between 9.9 and 15.8 atomic%, d between 2.5 and 8.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. Composant d'habillage (1) selon la revendication 21, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 14.8 et 15.8% atomique, d compris entre 2.5 et 3.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100.Cladding component (1) according to claim 21, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r between 49.2 and 50.2 at%, s between 31.4 and 32.5 at% , c between 14.8 and 15.8 atomic%, d between 2.5 and 3.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. Composant d'habillage (1) selon la revendication 21, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 11.8 et 12.8% atomique, d compris entre 5.5 et 6.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100.Cladding component (1) according to claim 21, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r between 49.2 and 50.2 at%, s between 31.4 and 32.5 at% , c between 11.8 and 12.8 atomic%, d between 5.5 and 6.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. Composant d'habillage (1) selon la revendication 21, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 9.9 et 10.9% atomique, d compris entre 7.7 et 8.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100.Cladding component (1) according to claim 21, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r between 49.2 and 50.2 at%, s between 31.4 and 32.5 at% , between 9.9 and 10.9 atomic%, d between 7.7 and 8.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFeeCuf, avec r compris entre 49.5 et 50.5% atomique, s compris entre 31.5 et 32.5% atomique, e compris entre 16.5 et 17.5% atomique, f compris entre 0.5 et 1.5% atomique, avec r+s+e+f=100.Trim component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe e Cu f, with r comprised between 49.5 and 50.5 atomic%, s between 31.5 and 32.5 atomic% between 16.5 and 17.5 atomic%, f between 0.5 and 1.5 atomic%, with r + s + e + f = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFegZrh, avec r compris entre 48.5 et 49.5% atomique, s compris entre 31.8 et 32.8% atomique, g compris entre 17.2 et 18.2% atomique, h compris entre 0.5 et 1.5% atomique, avec r+s+g+h=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe g Zr h , with r between 48.5 and 49.5 at%, s between 31.8 and 32.8 at% , g between 17.2 and 18.2 at%, h between 0.5 and 1.5 atomic%, with r + s + g + h = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFejAlk, avec r compris entre 48.5 et 49.5% atomique, s compris entre 31.2 et 32.2% atomique, j compris entre 16.8 et 17.8% atomique, k compris entre 1.5 et 2.5% atomique, avec r+s+j+k=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe j Al k , with r between 48.5 and 49.5 at%, s between 31.2 and 32.2 at% , between 16.8 and 17.8 atomic%, k between 1.5 and 2.5 atomic%, with r + s + j + k = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que ledit alliage obéit à la composition atomique TirPdsFemNbn, avec r compris entre 44.0 et 45.0 % atomique, s compris entre 34.5 et 35.5% atomique, m compris entre 9.0 et 10.0% atomique, n compris entre 10.5 et 11.5% atomique, avec r+s+m+n=100.Cladding component (1) according to claim 12, characterized in that said alloy obeys the atomic composition Ti r Pd s Fe m Nb n , with r ranging between 44.0 and 45.0 at%, s between 34.5 and 35.5 at% , m between 9.0 and 10.0 at%, n between 10.5 and 11.5 at%, with r + s + m + n = 100. Composant d'habillage (1) selon la revendication 12, caractérisé en ce que M comporte un ou plusieurs éléments pris parmi un cinquième groupe comportant : Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.Cladding component (1) according to claim 12, characterized in that M comprises one or more elements taken from a fifth group comprising: Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge , Sn, In. Composant d'habillage (1) selon la revendication 29, caractérisé en ce que lequel M comporte Fe et/ou Nb comme éléments majoritaires.Cladding component (1) according to claim 29, characterized in that M comprises Fe and / or Nb as majority elements. Composant d'habillage (1) selon la revendication 30, caractérisé en ce que ledit alliage comporte 50% en masse de palladium.Cladding component (1) according to claim 30, characterized in that said alloy comprises 50% by weight of palladium. Pièce d'horlogerie (10) ou de bijouterie comportant au moins un composant d'habillage (1) selon l'une des revendications précédentes.Timepiece (10) or jewelery comprising at least one dressing component (1) according to one of the preceding claims.
EP14200381.3A 2014-12-29 2014-12-29 Timepiece or piece of jewellery made of a light titanium-based precious alloy Withdrawn EP3040790A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
EP14200381.3A EP3040790A1 (en) 2014-12-29 2014-12-29 Timepiece or piece of jewellery made of a light titanium-based precious alloy
PCT/EP2015/080270 WO2016107755A1 (en) 2014-12-29 2015-12-17 Lightweight precious alloy made from titanium and gold, and timepiece or jewellery item component made from a lightweight precious alloy of titanium and gold
CN201580028804.5A CN106460094B (en) 2014-12-29 2015-12-17 The lightweight noble alloy made of titanium and gold and timer or jewelry part made of the lightweight noble alloy of the titanium and gold
PCT/EP2015/080211 WO2016107752A1 (en) 2014-12-29 2015-12-17 Timepiece or jewellery item made from lightweight precious alloy comprising titanium
JP2017507083A JP6389561B2 (en) 2014-12-29 2015-12-17 Gold and titanium light noble metal alloys, and timer or jewelry parts made of such gold and titanium light noble metal alloys
EP15817229.6A EP3240915B1 (en) 2014-12-29 2015-12-17 Lightweight precious alloy made from titanium and gold, and timepiece or jewellery item component made from a lightweight precious alloy of titanium and gold
US15/308,185 US10136708B2 (en) 2014-12-29 2015-12-17 Light precious alloy of gold and titanium and components for timepieces or jewellery made from such a light precious alloy of gold and titanium
EP15810677.3A EP3241078B1 (en) 2014-12-29 2015-12-17 Timepiece or jewellery item made from lightweight precious alloy comprising titanium
CN201580071445.1A CN107208187B (en) 2014-12-29 2015-12-17 Clock and watch or jewelry made of the lightweight precious metal alloys comprising titanium
US15/533,471 US10206465B2 (en) 2014-12-29 2015-12-17 Timepiece or piece of jewellery made of a light precious alloy containing titanium
JP2017546041A JP6514354B2 (en) 2014-12-29 2015-12-17 A timepiece or ornament made of light noble alloy containing titanium
HK18103140.3A HK1243743B (en) 2014-12-29 2018-03-05 Timepiece or jewellery item made fromlightweight precious alloy comprising titanium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP14200381.3A EP3040790A1 (en) 2014-12-29 2014-12-29 Timepiece or piece of jewellery made of a light titanium-based precious alloy

Publications (1)

Publication Number Publication Date
EP3040790A1 true EP3040790A1 (en) 2016-07-06

Family

ID=52130164

Family Applications (3)

Application Number Title Priority Date Filing Date
EP14200381.3A Withdrawn EP3040790A1 (en) 2014-12-29 2014-12-29 Timepiece or piece of jewellery made of a light titanium-based precious alloy
EP15810677.3A Active EP3241078B1 (en) 2014-12-29 2015-12-17 Timepiece or jewellery item made from lightweight precious alloy comprising titanium
EP15817229.6A Active EP3240915B1 (en) 2014-12-29 2015-12-17 Lightweight precious alloy made from titanium and gold, and timepiece or jewellery item component made from a lightweight precious alloy of titanium and gold

Family Applications After (2)

Application Number Title Priority Date Filing Date
EP15810677.3A Active EP3241078B1 (en) 2014-12-29 2015-12-17 Timepiece or jewellery item made from lightweight precious alloy comprising titanium
EP15817229.6A Active EP3240915B1 (en) 2014-12-29 2015-12-17 Lightweight precious alloy made from titanium and gold, and timepiece or jewellery item component made from a lightweight precious alloy of titanium and gold

Country Status (6)

Country Link
US (2) US10136708B2 (en)
EP (3) EP3040790A1 (en)
JP (2) JP6389561B2 (en)
CN (2) CN107208187B (en)
HK (1) HK1243743B (en)
WO (2) WO2016107752A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3572549A1 (en) 2018-05-24 2019-11-27 Richemont International S.A. Jewellery item

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109881044B (en) * 2019-04-11 2021-07-27 福建工程学院 High-hardness and high-wear-resistance titanium alloy and preparation method and application thereof
EP3889691B1 (en) * 2019-05-07 2024-02-21 Nivarox-FAR S.A. Horological hairspring made of a nb-hf alloy
CN110284021B (en) * 2019-06-27 2020-06-30 袁海 Intermediate alloy for improving hardness of pure gold and pure silver and preparation method and application thereof
EP3800511B1 (en) * 2019-10-02 2022-05-18 Nivarox-FAR S.A. Pivoting shaft for a regulating organ
CN112813299A (en) * 2019-11-12 2021-05-18 新疆大学 High-strength low-cost corrosion-resistant titanium alloy
CN111020272A (en) * 2019-12-14 2020-04-17 深圳晶辉应用材料有限公司 High-performance gold-based silver-palladium alloy bonding material
EP4026923A1 (en) 2021-01-07 2022-07-13 Officine Panerai AG Gold and titanium based alloy
CN115178913B (en) * 2022-09-13 2023-01-10 中国航发北京航空材料研究院 Brazing filler metal and preparation method and brazing method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0239747A1 (en) * 1986-03-12 1987-10-07 Sumitomo Electric Industries, Ltd. Function alloy and method of producing the same
EP0267318A2 (en) * 1986-11-13 1988-05-18 C. HAFNER GmbH &amp; Co. Alloy for ornamental purposes
CH704233A1 (en) * 2010-12-17 2012-06-29 Richemont Int Sa Outer part of a casing for a watch, where outer part is made of quasi-beta titanium alloy that is subjected to a hardening treatment comprising heating the alloy at a specified value, quenching and then tempering to obtain a hardness

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB876887A (en) 1957-07-12 1961-09-06 Degussa Gold alloys, for use as material for electric resistances
US4851058A (en) * 1982-09-03 1989-07-25 General Motors Corporation High energy product rare earth-iron magnet alloys
JPH02225655A (en) * 1989-02-28 1990-09-07 Agency Of Ind Science & Technol Gold alloy capable of coloring into bright black color and coloring method therefor
JPH03110046A (en) * 1989-09-26 1991-05-10 Tokin Corp Alloy fine wire and production thereof
JPH06145843A (en) * 1992-11-10 1994-05-27 Tokin Corp Burn-in test element and burn-in tester
DE4306542A1 (en) 1993-01-14 1994-07-21 Sunder Plassmann Paul Dr Gold@-titanium@ alloys used for dental restoration work
TW360716B (en) * 1993-02-19 1999-06-11 Citizen Watch Co Ltd Golden decorative part and process for producing the same
US5617377A (en) * 1995-12-13 1997-04-01 Perret, Jr.; Gerard A. Watchband connector pin utilizing shape memory material
CN1061384C (en) * 1998-04-25 2001-01-31 湖北金兰首饰集团有限公司 Ultrastrong high-purity gold alloy material for jewelry
JPH11310836A (en) * 1998-04-30 1999-11-09 Tanaka Kikinzoku Kogyo Kk Age-hardening material for ornament
US6675610B2 (en) * 1999-12-23 2004-01-13 Guy Beard Jewelry including shape memory alloy elements
US6849344B2 (en) * 2002-09-25 2005-02-01 Titanium Metals Corp. Fabricated titanium article having improved corrosion resistance
GB0419062D0 (en) * 2004-08-27 2004-09-29 Johnson Matthey Plc Platinum alloy catalyst
US20060231171A1 (en) * 2005-04-19 2006-10-19 Davis Samuel A Method for adding boron to metal alloys
CH697875B1 (en) 2005-07-16 2009-03-13 Ludwig Mueller precious metal alloy.
CN100543166C (en) * 2006-10-13 2009-09-23 北京航空航天大学 The alloy and the utensil that contain micro element
JP5079555B2 (en) * 2008-03-17 2012-11-21 シチズンホールディングス株式会社 Decorative parts
SG160266A1 (en) 2008-09-08 2010-04-29 Autium Pte Ltd Coloured gold alloy and method for forming the same
US8361250B2 (en) * 2009-02-13 2013-01-29 California Institute Of Technology Amorphous platinum-rich alloys
CN103534369B (en) * 2011-05-02 2016-11-16 洛桑联邦理工学院 Platinum base alloy
PT2546371T (en) 2011-07-12 2017-02-14 Cendres + Métaux Sa 18-carat grey gold
CH707539B1 (en) 2013-02-06 2017-01-13 Rolex Sa Pink gold alloy for timepiece.
JP6156865B2 (en) * 2013-02-07 2017-07-05 国立研究開発法人物質・材料研究機構 Super elastic alloy

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0239747A1 (en) * 1986-03-12 1987-10-07 Sumitomo Electric Industries, Ltd. Function alloy and method of producing the same
EP0267318A2 (en) * 1986-11-13 1988-05-18 C. HAFNER GmbH &amp; Co. Alloy for ornamental purposes
CH704233A1 (en) * 2010-12-17 2012-06-29 Richemont Int Sa Outer part of a casing for a watch, where outer part is made of quasi-beta titanium alloy that is subjected to a hardening treatment comprising heating the alloy at a specified value, quenching and then tempering to obtain a hardness

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3572549A1 (en) 2018-05-24 2019-11-27 Richemont International S.A. Jewellery item

Also Published As

Publication number Publication date
CN107208187B (en) 2019-02-19
US20170226613A1 (en) 2017-08-10
EP3240915B1 (en) 2020-07-08
EP3240915A1 (en) 2017-11-08
HK1243743B (en) 2020-03-20
EP3241078A1 (en) 2017-11-08
CN106460094B (en) 2019-05-14
WO2016107755A1 (en) 2016-07-07
JP2018503480A (en) 2018-02-08
US20170367446A1 (en) 2017-12-28
JP2017518442A (en) 2017-07-06
US10136708B2 (en) 2018-11-27
WO2016107752A4 (en) 2016-09-15
US10206465B2 (en) 2019-02-19
CN107208187A (en) 2017-09-26
JP6389561B2 (en) 2018-09-12
CN106460094A (en) 2017-02-22
EP3241078B1 (en) 2021-05-26
JP6514354B2 (en) 2019-05-15
WO2016107752A1 (en) 2016-07-07

Similar Documents

Publication Publication Date Title
EP3241078B1 (en) Timepiece or jewellery item made from lightweight precious alloy comprising titanium
EP3543368B1 (en) High-entropy alloys for covering components
EP3077561B1 (en) Bulk amorphous alloy made of beryllium-free zirconium
EP3128035B1 (en) Bulk amorphous alloy made of nickel-free zirconium
EP3519900B1 (en) Timepiece component having a high-entropy alloy
EP2588635B1 (en) Gold alloy with improved hardness
CH714802A2 (en) High entropy alloys for dressing components.
EP2546371B1 (en) 18-carat grey gold
EP2914759B1 (en) Edelstahllegierung ohne nickel
CH710562A2 (en) Cladding component for timepiece or jewelry piece in a light titanium-based precious alloy.
EP3020835B1 (en) Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy
CH708928A2 (en) Solid amorphous alloy based on beryllium-free zirconium.
CH707203B1 (en) Stainless steel alloy without nickel.
CH718454A2 (en) Spiral spring for a clock movement and process for manufacturing this spiral spring.
CH703143B1 (en) Palladium-based alloy, useful in jewelry article, comprises palladium, aluminum, and at least one additional metal or germanium

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

17P Request for examination filed

Effective date: 20170109

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

17Q First examination report despatched

Effective date: 20170307

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20170619