EP3128035B1 - Bulk amorphous alloy made of nickel-free zirconium - Google Patents

Bulk amorphous alloy made of nickel-free zirconium Download PDF

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Publication number
EP3128035B1
EP3128035B1 EP15179473.2A EP15179473A EP3128035B1 EP 3128035 B1 EP3128035 B1 EP 3128035B1 EP 15179473 A EP15179473 A EP 15179473A EP 3128035 B1 EP3128035 B1 EP 3128035B1
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Prior art keywords
equal
nickel
amorphous alloy
alloys
zirconium
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German (de)
French (fr)
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EP3128035A1 (en
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Alban Dubach
Yves Winkler
Tommy Carozzani
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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 EP15179473.2A priority Critical patent/EP3128035B1/en
Priority to US15/188,588 priority patent/US9933754B2/en
Priority to JP2016137321A priority patent/JP6313821B2/en
Priority to CN201610608175.XA priority patent/CN106399871B/en
Publication of EP3128035A1 publication Critical patent/EP3128035A1/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • 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
    • 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
    • C22C1/11—Making amorphous alloys

Definitions

  • the invention relates to a solid amorphous alloy.
  • the invention also relates to a timepiece component made of such an alloy.
  • the invention also relates to a watch comprising at least one such component.
  • the invention relates to the fields of watchmaking, jewelery, and fine jewelry, in particular for structures: watch cases, middle parts, plates, glasses, pushers, crowns, buckles, bracelets, rings, earrings. and others.
  • Amorphous alloys are more and more used in the fields of watchmaking, jewelry, and fine jewelry, in particular for structures: watch cases, casebands, plates, glasses, pushers, crowns, buckles, bracelets, and others.
  • Amorphous alloys based on zirconium without nickel and without beryllium generally show critical diameters which are smaller than those of alloys with nickel and beryllium, which is unfavorable for the production of solid parts. It is therefore a question of developing alloys such that the critical diameter D c * is sufficiently large.
  • the invention proposes to produce massive amorphous alloys based on zirconium, either nickel-free, or both nickel-free and beryllium-free, for watchmaking applications.
  • the invention proposes to increase the critical diameter of amorphous alloys based on zirconium at least without nickel, or even at the same time without nickel and without beryllium, while keeping a high value of ⁇ Tx (difference between the crystallization temperature Tx and the glass transition temperature Tg).
  • the invention relates to a solid amorphous alloy based on zirconium or / and hafnium, free of nickel, with the addition of other elements to increase its critical diameter, according to claim 1.
  • the invention also relates to a timepiece or jewelry component made of such an alloy.
  • the invention relates to the fields of watchmaking, jewelery, and fine jewelry, in particular for structures: watch cases, middle parts, plates, glasses, pushers, crowns, buckles, bracelets, rings, earrings. and others.
  • the invention proposes to produce massive amorphous alloys based on zirconium without nickel, or at the same time without nickel and without beryllium, for watchmaking applications, these alloys according to the invention being designed to have properties similar to those of alloys amorphous containing nickel, or containing nickel and beryllium.
  • the invention proposes to increase the critical diameter of amorphous zirconium alloys at least without nickel, or at the same time without nickel and without beryllium, while keeping a high value of ⁇ Tx.
  • free of Z is meant that, in the alloy, the content of Z is preferably zero, if not very low, in the same way as impurities, and preferably less than or equal to 0.1%.
  • a nickel-free alloy that is to say containing less than 0.1% in atomic%, of nickel, and “alloy without nickel and beryllium-free ”an alloy containing less than 0.1%, in atomic%, of nickel and comprising less than 0.1%, in atomic%, of beryllium.
  • alloys which include nickel substitute elements, or both nickel and beryllium, which do not pose any problem in contact with the skin, alloys which have values of the critical diameter D c * and the interval ⁇ Tx.
  • the invention relates to a solid amorphous alloy based on zirconium, nickel free, with the addition of certain specific components to increase the critical diameter D c *.
  • the experimentation carried out within the framework of the present invention makes it possible to establish that the possibility of a good production of a timepiece covering component, of a given thickness E, produced in an amorphous alloy, is closely associated with the critical diameter D c * of this amorphous alloy.
  • maximum advantage is taken of the critical diameter D c *.
  • the critical diameter D c * is greater than 1.8 times the thickness E. More particularly, the critical diameter D c * is close to twice the thickness E, in particular between 1.8 E and 2.2 E.
  • a family of zirconium alloys comprising at least copper and aluminum, in particular Zr-Cu-Al and Zr-Cu-Al-Ag is described in the document "Mater Trans, Vol 48, No 7 (2007) 1626-1630" . Its known properties are the increase in the critical diameter from 8mm to 12mm, by adding silver to the alloy, for example by transforming a Zr 46 Cu 46 Al 8 alloy into a Zr 42 Cu 42 Al 8 Ag 8 alloy. Due to the high percentage of copper (Cu / Zr ratio ⁇ 1), the corrosion resistance of this family of alloys is very poor and these compositions even have a tendency to discolour or darken over time at room temperature. The compositions do not contain iron.
  • a family of zirconium-based alloys comprising at least titanium, copper and aluminum, in particular Zr-Ti-Cu-Al and Zr-Ti-Nb-Cu-Al, is known from the document US2013032252 .
  • the alloys Zr 45-69 Ti 0.25-8 Cu 21 - 35 Al 7.5-15 , and Zr 45-69 (Nb, Ti) 0.25-15 Cu 21-35 Al 7.5-13 with 0.25 ⁇ Ti ⁇ 8 are known in particular .
  • the compositions do not contain iron.
  • the critical diameter disclosed is less than 10mm. It suits to emphasize that the values displayed in the literature do not always correspond to reality.
  • a family of zirconium alloys comprising at least palladium, copper and aluminum, of the Zr-Cu-Pd-Al type is known from the document WO2004022118 , which discloses a composition with 10% palladium, therefore of high price. The critical diameter remains quite small. The composition does not contain iron.
  • a family of zirconium alloys comprising at least niobium, copper and aluminum, of the Zr-Nb-Cu-Al type is known from the document WO2013075829 .
  • This family allows the manufacture of amorphous alloys using elements which are not very pure, for example with the use of industrial zirconium instead of pure zirconium. Consequently, the compositions also contain traces of Fe, Co, Hf and O: Zr 64.2-72 Hf 0.01-3.3 (Fe, Co) 0.01-0.15 Nb 1.3-2.4 O 0.01-0.13 Cu 23.3-25.5 Al 3.4-4.2 (% by mass).
  • the critical diameter is close to 5mm.
  • a family of zirconium-based alloys comprising at least niobium, copper, palladium and aluminum, of the Zr-Nb-Cu-Pd-Al type is known from the document "J Mech Behav Biomed, Vol 13 (2012) 166-173" , which deals with the development of amorphous alloys in the Zr 45 + x Cu 40-x Al 7 Pd 5 Nb 3 system .
  • the compositions do not contain iron.
  • the tests carried out in the context of the development of the invention have shown that these compositions of the Zr-Nb-Cu-Pd-Al type do not resist corrosion.
  • a family of zirconium-based alloys comprising at least copper, iron, aluminum, and silver, of the Zr-Cu-Fe-Al-Ag type is known from the document. "MSEA, Vol 527 (2010) 1444-1447” , which studies the influence of Fe on the thermophysical properties of the alloy (Zr 46 Cu 39.2 Ag 7.8 Al 7 ) 100-y Fe y with 0 ⁇ y ⁇ 7. The Cu / Zr ratio is high, and therefore the corrosion resistance is not good.
  • a family of zirconium alloys comprising at least copper, iron, aluminum, and silver, of the Zr-Cu-Fe-Al-X type, with X being at least one element of the family Ti, Hf, V, Nb, Y, Cr, Mo, Fe, Co, Sn, Zn, P, Pd, Ag, Au, Pt, is known from the document WO2006026882 relating to the alloy Zr 33-81 Cu 6-45 (Fe, Co) 3-15 Al 5-21 -X 0-6 .
  • the invention comprises only alloys comprising at least 0.5% iron.
  • the Zr-Cu-Fe-Al system is chosen as a starting point, because the literature teaches that this system has a relatively high vitrification ability (GFA, glass-forming ability) (greater than for ternary alloys Zr-Cu-AI).
  • the critical diameter of the Zr-Cu-Fe-Al quaternary alloys is not yet large enough to produce massive cladding pieces, such as a middle part or the like.
  • the objective with a critical diameter D c * close to 9 mm, or greater than this value, takes into account the fact that, at least in fine watchmaking, the thickness of a middle part is typically close to 5mm.
  • X being at least one element of the family Ti, Hf, V, Nb, Y, Cr, Mo, Fe, Co, Sn , Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os.
  • compositions 1 and 2 are known, do not comprise any additional component X, and correspond to the teachings of the document WO2006026882 .
  • compositions 3 and 4 relate to compositions which have not been disclosed in the literature, however, they are covered by certain ranges disclosed by the document. WO2006026882 .
  • Composition 3 comprises a unique additional component X which is silver, the critical diameter is better than that of compositions 1 and 2, but insufficient to satisfy the specifications of the invention.
  • Composition 4 has two additional X components, niobium and silver, with a total% of 6, and the critical diameter is of the same order as that of sample 3.
  • the test campaign shows that the only way to significantly increase the critical diameter D c * is to have at least two components X in the alloy, and with a% greater than or equal to 6.3.
  • compositions 5-12 are entirely new, and do not overlap with the ranges of the prior art. Among them, compositions 5 to 11 have a critical diameter D c * greater than or equal to 9.5 mm. Composition 12 shows that a cumulative percentage “a” of the components X greater than a certain value, in this case 10% in atomic percentage, does not bring any beneficial effect, on the contrary even, since the critical diameter D c * is significantly lower than the previous ones.
  • the results show that the addition of elements X increases the critical diameter D c * and that ideally it is necessary to add at least two elements X to maximize their effect.
  • the tests show that the critical diameter D c * is maximum when the cumulative percentage "a" of the elements X is between 6 and 10%.
  • the first filler metal and the second filler metal are taken from the family comprising Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, and Hf when said base n 'does not, and Zr when said base does not, with the cumulative atomic percentage of these at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0.
  • the first filler metal and the second filler metal are taken from the family comprising Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, with the cumulative atomic percentage of these at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0.
  • the alloy according to the invention comprises only zirconium and no hafnium.
  • the alloy according to the invention comprises only hafnium and no zirconium.
  • the alloy according to the invention is free of nickel and beryllium.
  • the alloy according to the invention is free of cobalt and / or chromium.
  • the alloys according to the invention resist corrosion, and have a stable color (no tarnishing or discoloration when worn)
  • the invention also relates to a component 1 of timepieces or jewelry made of such an amorphous alloy.
  • the critical diameter D c * of the amorphous alloy according to the invention, which constitutes this component, is greater than 1.8 times the greatest thickness E of this component 1.
  • the invention also relates to a watch 2 comprising at least one such covering component 1.
  • this watch 2 comprises such a covering component 1 which is a middle part of maximum thickness E between 4.0 and 5.0 mm produced in such an amorphous alloy having a critical diameter D c * greater than 8 mm.

Description

Domaine de l'inventionField of the invention

L'invention concerne un alliage amorphe massif.The invention relates to a solid amorphous alloy.

L'invention concerne encore un composant d'horlogerie réalisé en un tel alliage.The invention also relates to a timepiece component made of such an alloy.

L'invention concerne encore une montre comportant au moins un tel composant.The invention also relates to a watch comprising at least one such component.

L'invention concerne les domaines de l'horlogerie, de la bijouterie, et de la joaillerie, en particulier pour les structures : boîtes de montres, carrures, platines, lunettes, poussoirs, couronnes, boucles, bracelets, bagues, boucles d'oreilles et autres.The invention relates to the fields of watchmaking, jewelery, and fine jewelry, in particular for structures: watch cases, middle parts, plates, glasses, pushers, crowns, buckles, bracelets, rings, earrings. and others.

Arrière-plan de l'inventionInvention background

Les alliages amorphes sont de plus en plus utilisés dans les domaines de l'horlogerie, de la bijouterie, et de la joaillerie, en particulier pour les structures : boîtes de montres, carrures, platines, lunettes, poussoirs, couronnes, boucles, bracelets, et autres.Amorphous alloys are more and more used in the fields of watchmaking, jewelry, and fine jewelry, in particular for structures: watch cases, casebands, plates, glasses, pushers, crowns, buckles, bracelets, and others.

Les composants à usage externe, destinés à être en contact avec la peau de l'utilisateur, doivent obéir à certaines contraintes, en particulier en raison de la toxicité ou des effets allergènes de certains métaux, notamment le béryllium et le nickel. Malgré les qualités intrinsèques particulières de tels métaux, on s'attache à mettre sur le marché, au moins pour les composants susceptibles d'entrer en contact avec l'épiderme de l'utilisateur, des alliages comportant peu voire pas de béryllium ou de nickel.The components for external use, intended to be in contact with the skin of the user, must obey certain constraints, in particular because of the toxicity or allergenic effects of certain metals, in particular beryllium and nickel. Despite the specific intrinsic qualities of such metals, efforts are being made to market, at least for components liable to come into contact with the user's epidermis, alloys comprising little or no beryllium or nickel .

Les alliages amorphes massifs à base de zirconium sont connus depuis les années 90. Les publications suivantes concernent de tels alliages:

  1. [1] Zhang, et al., Amorphous Zr-Al-TM (TM=Co, Ni, Cu) Alloys with Significant Supercooled Liquid Region of Over 100 K, Materials Transactions, JIM, Vol. 32, No. 11 (1991) pp. 1005-1010 .
  2. [2] Lin, et al., Effect of Oxygen Impurity on Crystallization of an Undercooled Bulk Glass Forming Zr-Ti-Cu-Ni-Al Alloy, Materials Transactions, JIM, Vol. 38, No. 5 (1997) pp. 473-477 .
  3. [3] Brevet US6592689 .
  4. [4] Inoue, et al., Formation, Thermal Stability and Mechanical Properties of Bulk Glassy Alloys with a Diameter of 20 mm in Zr-(Ti,Nb)-Al-Ni-Cu System, Materials Transactions, JIM, Vol. 50, No. 2 (2009) pp. 388-394 .
  5. [5] Demande de brevet US 2012/0247948 A1 .
  6. [6] Inoue et al., "Recent development and application products of bulk glassy alloys", ACTA MATERIALIA, Vol. 59, No. 6 (2010), pp. 2243-2267 .
Massive amorphous alloys based on zirconium have been known since the 1990s. The following publications relate to such alloys:
  1. [1] Zhang, et al., Amorphous Zr-Al-TM (TM = Co, Ni, Cu) Alloys with Significant Supercooled Liquid Region of Over 100 K, Materials Transactions, JIM, Vol. 32, No. 11 (1991) pp. 1005-1010 .
  2. [2] Lin, et al., Effect of Oxygen Impurity on Crystallization of an Undercooled Bulk Glass Forming Zr-Ti-Cu-Ni-Al Alloy, Materials Transactions, JIM, Vol. 38, No. 5 (1997) pp. 473-477 .
  3. [3] Patent US6592689 .
  4. [4] Inoue, et al., Formation, Thermal Stability and Mechanical Properties of Bulk Glassy Alloys with a Diameter of 20 mm in Zr- (Ti, Nb) -Al-Ni-Cu System, Materials Transactions, JIM, Vol. 50, No. 2 (2009) pp. 388-394 .
  5. [5] Patent application US 2012/0247948 A1 .
  6. [6] Inoue et al., "Recent development and application products of bulk glassy alloys", ACTA MATERIALIA, Vol. 59, No. 6 (2010), pp. 2243-2267 .

Les alliages amorphes avec les meilleures aptitudes à la vitrification, aptitude couramment désignée sous le vocable GFA utilisé ci-après (« glass-forming ability»), et liée au diamètre critique Dc*, se trouvent dans les systèmes :

  • Zr-Ti-Cu-Ni-Be,
  • et Zr-Cu-Ni-Al.
The amorphous alloys with the best vitrification aptitudes, aptitude commonly designated under the term GFA used below (“glass-forming ability”), and linked to the critical diameter D c *, are found in the systems:
  • Zr-Ti-Cu-Ni-Be,
  • and Zr-Cu-Ni-Al.

Les compositions (en % atomique) des alliages les plus souvent utilisés/caractérisés sont listées ci-dessous :

  • Zr44Ti11Cu9.8Ni10.2Be25 (LM1b)
  • Zr65Cu17.5Ni10Al7.5 [1]
  • Zr52.5Cu17.9Ni14.6Al10Ti5 (Vit105) [2]
  • Zr57Cu15.4Ni12.6Al10Nb5 (Vit106) et Zr58.5Cu15.6Ni12.8Al10.3Nb2.8 (Vit106a) [3]
  • Zr61Cu17.5Ni10Al7.5Ti2Nb2 [4]
  • Zr62.5Cu22.5Al10Fe5 [5], [6]
The compositions (in atomic%) of the most often used / characterized alloys are listed below:
  • Zr44Ti11Cu9.8Ni10.2Be25 (LM1b)
  • Zr65Cu17.5Ni10Al7.5 [1]
  • Zr52.5Cu17.9Ni14.6Al10Ti5 (Vit105) [2]
  • Zr57Cu15.4Ni12.6Al10Nb5 (Vit106) and Zr58.5Cu15.6Ni12.8Al10.3Nb2.8 (Vit106a) [3]
  • Zr61Cu17.5Ni10Al7.5Ti2Nb2 [4]
  • Zr62.5Cu22.5Al10Fe5 [5], [6]

Vu le potentiel allergène du nickel, ces alliages ne sont pas utilisables pour des applications en contact avec la peau, comme des pièces d'habillage ou similaire. En plus, à cause de la toxicité du béryllium la fabrication et l'usinage de certains de ces alliages nécessitent des mesures de précaution spéciales. C'est dommage, car ces deux éléments stabilisent la phase amorphe, et facilitent l'obtention d'alliages ayant un diamètre critique Dc* élevé. De plus, le nickel a un effet positif sur la résistance à la corrosion des alliages amorphes à base de zirconium.Given the allergenic potential of nickel, these alloys cannot be used for applications in contact with the skin, such as trim pieces or the like. In addition, because of the toxicity of beryllium, the manufacture and machining of some of these alloys requires special precautionary measures. It is a shame, because these two elements stabilize the amorphous phase, and facilitate the obtaining of alloys with a high critical diameter D c *. In addition, nickel has a positive effect on the corrosion resistance of amorphous zirconium alloys.

Les alliages amorphes à base zirconium sans nickel et sans béryllium montrent en général des diamètres critiques qui sont inférieurs à ceux des alliages avec nickel et béryllium, ce qui est défavorable pour la réalisation de pièces massives. Il s'agit donc de mettre au point des alliages tels que le diamètre critique Dc* soit suffisamment important.Amorphous alloys based on zirconium without nickel and without beryllium generally show critical diameters which are smaller than those of alloys with nickel and beryllium, which is unfavorable for the production of solid parts. It is therefore a question of developing alloys such that the critical diameter D c * is sufficiently large.

Résumé de l'inventionSummary of the invention

L'invention se propose de réaliser des alliages amorphes massifs à base de zirconium, ou bien sans nickel, ou bien à la fois sans nickel et sans béryllium, pour des applications horlogères.The invention proposes to produce massive amorphous alloys based on zirconium, either nickel-free, or both nickel-free and beryllium-free, for watchmaking applications.

L'invention se propose d'augmenter le diamètre critique des alliages amorphes à base zirconium au moins sans nickel, ou encore à la fois sans nickel et sans béryllium, tout en gardant une valeur élevée de ΔTx (différence entre la température de cristallisation Tx et la température de transition vitreuse Tg).The invention proposes to increase the critical diameter of amorphous alloys based on zirconium at least without nickel, or even at the same time without nickel and without beryllium, while keeping a high value of ΔTx (difference between the crystallization temperature Tx and the glass transition temperature Tg).

L'invention concerne un alliage amorphe massif à base de zirconium ou/et de hafnium, exempt de nickel, avec rajout d'autres éléments pour augmenter son diamètre critique, selon la revendication 1.The invention relates to a solid amorphous alloy based on zirconium or / and hafnium, free of nickel, with the addition of other elements to increase its critical diameter, according to claim 1.

L'invention concerne encore un composant d'horlogerie ou de joaillerie réalisé en un tel alliage.The invention also relates to a timepiece or jewelry component made of such an alloy.

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 représente, de façon schématisée, la mesure du diamètre critique Dc* dans un échantillon conique ;
  • la figure 2 représente, de façon schématisée, une pièce d'horlogerie réalisée en un alliage selon l'invention.
Other characteristics and advantages of the invention will appear on reading the detailed description which follows, with reference to the appended drawings, where:
  • the figure 1 represents, schematically, the measurement of the critical diameter D c * in a conical sample;
  • the figure 2 shows, schematically, a timepiece made of an alloy according to the invention.

Description détaillée des modes de réalisation préférésDetailed description of preferred embodiments

L'invention concerne les domaines de l'horlogerie, de la bijouterie, et de la joaillerie, en particulier pour les structures : boîtes de montres, carrures, platines, lunettes, poussoirs, couronnes, boucles, bracelets, bagues, boucles d'oreilles et autres.The invention relates to the fields of watchmaking, jewelery, and fine jewelry, in particular for structures: watch cases, middle parts, plates, glasses, pushers, crowns, buckles, bracelets, rings, earrings. and others.

L'invention se propose de réaliser des alliages amorphes massifs à base de zirconium sans nickel, ou à la fois sans nickel et sans béryllium, pour des applications horlogères, ces alliages selon l'invention étant conçus pour présenter des propriétés analogues à celles des alliages amorphes contenant du nickel, ou contenant du nickel et du béryllium.The invention proposes to produce massive amorphous alloys based on zirconium without nickel, or at the same time without nickel and without beryllium, for watchmaking applications, these alloys according to the invention being designed to have properties similar to those of alloys amorphous containing nickel, or containing nickel and beryllium.

L'invention se propose d'augmenter le diamètre critique des alliages amorphes à base de zirconium au moins sans nickel, ou encore à la fois sans nickel et sans béryllium, tout en gardant une valeur élevée de ΔTx.The invention proposes to increase the critical diameter of amorphous zirconium alloys at least without nickel, or at the same time without nickel and without beryllium, while keeping a high value of ΔTx.

Par « exempt de Z » on entend que, dans l'alliage, la teneur de Z est, de préférence nulle, sinon très faible, au même titre que des impuretés, et de préférence inférieure ou égale à 0.1%.By "free of Z" is meant that, in the alloy, the content of Z is preferably zero, if not very low, in the same way as impurities, and preferably less than or equal to 0.1%.

On appellera ci-après « alliage sans nickel » un alliage exempt de nickel, c'est-à-dire comportant moins de 0.1% en % atomique, de nickel, et « alliage sans nickel et sans béryllium » un alliage comportant moins de 0.1%, en % atomique, de nickel et comportant moins de 0.1%, en % atomique, de béryllium.A nickel-free alloy, that is to say containing less than 0.1% in atomic%, of nickel, and “alloy without nickel and beryllium-free ”an alloy containing less than 0.1%, in atomic%, of nickel and comprising less than 0.1%, in atomic%, of beryllium.

Il s'agit donc d'élaborer une fabrication d'alliages, qui comportent des éléments de substitution au nickel, ou à la fois au nickel et au béryllium, qui ne posent pas de problème en contact avec la peau, alliages qui présentent des valeurs élevées du diamètre critique Dc* et de l'intervalle ΔTx.It is therefore a question of developing a production of alloys, which include nickel substitute elements, or both nickel and beryllium, which do not pose any problem in contact with the skin, alloys which have values of the critical diameter D c * and the interval ΔTx.

Aussi l'invention concerne un alliage amorphe massif à base de zirconium, sans nickel, avec rajout de certains composants particuliers pour augmenter le diamètre critique Dc*.Also the invention relates to a solid amorphous alloy based on zirconium, nickel free, with the addition of certain specific components to increase the critical diameter D c *.

En effet, l'expérimentation menée dans le cadre de la présente invention permet d'établir que la possibilité d'une bonne réalisation d'un composant d'habillage d'horlogerie, d'une épaisseur E donnée, réalisé dans un alliage amorphe, est étroitement associée au diamètre critique Dc* de cet alliage amorphe. Dans une exécution particulièrement avantageuse, on tire parti au maximum du diamètre critique Dc*. De façon préférée, le diamètre critique Dc* est supérieur à 1,8 fois l'épaisseur E. Plus particulièrement, le diamètre critique Dc* est voisin du double de l'épaisseur E, notamment compris entre 1.8 E et 2.2 E.In fact, the experimentation carried out within the framework of the present invention makes it possible to establish that the possibility of a good production of a timepiece covering component, of a given thickness E, produced in an amorphous alloy, is closely associated with the critical diameter D c * of this amorphous alloy. In a particularly advantageous embodiment, maximum advantage is taken of the critical diameter D c *. Preferably, the critical diameter D c * is greater than 1.8 times the thickness E. More particularly, the critical diameter D c * is close to twice the thickness E, in particular between 1.8 E and 2.2 E.

Différentes familles de compositions sans nickel sont déjà connues dans la littérature, mais avec des diamètres critiques faibles et/ou des mauvaises résistances à la corrosion.Different families of nickel-free compositions are already known in the literature, but with small critical diameters and / or poor corrosion resistance.

Une famille d'alliages de zirconium comportant au moins du cuivre et de l'aluminium, notamment Zr-Cu-Al et Zr-Cu-Al-Ag est décrite dans le document «Mater Trans, Vol 48, No 7 (2007) 1626-1630 » . Ses propriétés connues sont l'augmentation du diamètre critique de 8mm à 12mm, en rajoutant de l'argent dans l'alliage, par exemple en transformant un alliage Zr46Cu46Al8 en un alliage Zr42Cu42Al8Ag8. Du fait du pourcentage élevé de cuivre (rapport Cu/Zr ≈ 1), la résistance à la corrosion de cette famille d'alliages est très mauvaise et ces compositions ont même une tendance à se décolorer ou à noircir avec le temps à température ambiante. Les compositions ne contiennent pas de fer.A family of zirconium alloys comprising at least copper and aluminum, in particular Zr-Cu-Al and Zr-Cu-Al-Ag is described in the document "Mater Trans, Vol 48, No 7 (2007) 1626-1630" . Its known properties are the increase in the critical diameter from 8mm to 12mm, by adding silver to the alloy, for example by transforming a Zr 46 Cu 46 Al 8 alloy into a Zr 42 Cu 42 Al 8 Ag 8 alloy. Due to the high percentage of copper (Cu / Zr ratio ≈ 1), the corrosion resistance of this family of alloys is very poor and these compositions even have a tendency to discolour or darken over time at room temperature. The compositions do not contain iron.

Une famille d'alliages à base de zirconium comportant au moins du titane, du cuivre et de l'aluminium, notamment Zr-Ti-Cu-Al et Zr-Ti-Nb-Cu-Al, est connue par le document US2013032252 . On connaît en particulier les alliages Zr45-69Ti0.25-8Cu21-35Al7.5-15, et Zr45-69(Nb,Ti)0.25-15Cu21-35Al7.5-13 avec 0.25≤Ti≤8. Les compositions ne contiennent pas de fer. Le diamètre critique divulgué est inférieur à 10mm. Il convient de souligner que les valeurs affichées dans la littérature ne correspondent pas toujours à la réalité. Par exemple, dans le cas de ce document US2013032252 , les meilleures compositions se trouvent autour de Zr60-62Ti2Cu24-28Al10-12. La réalisation à titre de comparaison, menée lors de l'expérimentation de l'invention, selon le mode opératoire décrit ci-dessous, d'un alliage Zr61Ti2Cu26AI11 censé avoir un diamètre critique de 10mm, n'a permis d'obtenir qu'un diamètre critique Dc* de 4.5mm. Ceci incite à la plus grande méfiance à l'égard des résultats très optimistes affichés dans certains documents de l'art antérieur.A family of zirconium-based alloys comprising at least titanium, copper and aluminum, in particular Zr-Ti-Cu-Al and Zr-Ti-Nb-Cu-Al, is known from the document US2013032252 . The alloys Zr 45-69 Ti 0.25-8 Cu 21 - 35 Al 7.5-15 , and Zr 45-69 (Nb, Ti) 0.25-15 Cu 21-35 Al 7.5-13 with 0.25≤Ti≤8 are known in particular . The compositions do not contain iron. The critical diameter disclosed is less than 10mm. It suits to emphasize that the values displayed in the literature do not always correspond to reality. For example, in the case of this document US2013032252 , the best compositions are found around Zr60-62Ti2Cu24-28Al10-12. The realization by way of comparison, carried out during the experimentation of the invention, according to the operating mode described below, of an alloy Zr61Ti2Cu26AI11 supposed to have a critical diameter of 10mm, only allowed to obtain a critical diameter Dc * of 4.5mm. This incites the greatest distrust with regard to the very optimistic results displayed in certain documents of the prior art.

Une famille d'alliages de zirconium comportant au moins du palladium, du cuivre et de l'aluminium, de type Zr-Cu-Pd-Al est connue par le document WO2004022118 , qui divulgue une composition avec 10% de palladium, donc de prix élevé. Le diamètre critique reste assez petit. La composition ne contient pas de fer.A family of zirconium alloys comprising at least palladium, copper and aluminum, of the Zr-Cu-Pd-Al type is known from the document WO2004022118 , which discloses a composition with 10% palladium, therefore of high price. The critical diameter remains quite small. The composition does not contain iron.

Une famille d'alliages de zirconium comportant au moins du niobium, du cuivre et de l'aluminium, de type Zr-Nb-Cu-Al est connue par le document WO2013075829 . Cette famille permet la fabrication des alliages amorphes en utilisant des éléments pas très purs, par exemple avec une utilisation de zirconium industriel au lieu de zirconium pur. Par conséquent, les compositions contiennent également des traces de Fe, Co, Hf et O : Zr64.2-72Hf0.01-3.3(Fe,Co)0.01-0.15Nb1.3-2.4O0.01-0.13Cu23.3-25.5Al3.4-4.2 (% massique). Le diamètre critique est voisin de 5mm.A family of zirconium alloys comprising at least niobium, copper and aluminum, of the Zr-Nb-Cu-Al type is known from the document WO2013075829 . This family allows the manufacture of amorphous alloys using elements which are not very pure, for example with the use of industrial zirconium instead of pure zirconium. Consequently, the compositions also contain traces of Fe, Co, Hf and O: Zr 64.2-72 Hf 0.01-3.3 (Fe, Co) 0.01-0.15 Nb 1.3-2.4 O 0.01-0.13 Cu 23.3-25.5 Al 3.4-4.2 (% by mass). The critical diameter is close to 5mm.

Une famille d'alliages à base de zirconium comportant au moins du niobium, du cuivre, du palladium et de l'aluminium, de type Zr-Nb-Cu-Pd-Al est connue par le document « J Mech Behav Biomed, Vol 13 (2012) 166-173 » , qui traite du développement des alliages amorphes dans le système Zr45+xCu40-xAl7Pd5Nb3. Les compositions ne contiennent pas de fer. Les essais menés dans le cadre de la mise au point de l'invention ont montré que ces compositions de type Zr-Nb-Cu-Pd-Al ne résistent pas à la corrosion.A family of zirconium-based alloys comprising at least niobium, copper, palladium and aluminum, of the Zr-Nb-Cu-Pd-Al type is known from the document "J Mech Behav Biomed, Vol 13 (2012) 166-173" , which deals with the development of amorphous alloys in the Zr 45 + x Cu 40-x Al 7 Pd 5 Nb 3 system . The compositions do not contain iron. The tests carried out in the context of the development of the invention have shown that these compositions of the Zr-Nb-Cu-Pd-Al type do not resist corrosion.

Une famille d'alliages à base de zirconium comportant au moins du cuivre, du fer, de l'aluminium, et de l'argent, de type Zr-Cu-Fe-Al-Ag est connue par le document « MSEA, Vol 527 (2010) 1444-1447 » , qui étudie l'influence du Fe sur les propriétés thermophysiques de l'alliage (Zr46Cu39.2Ag7.8Al7)100-yFey avec 0<y<7. Le rapport Cu/Zr est élevé, et de fait la résistance à la corrosion n'est pas bonne. Une famille d'alliages de zirconium comportant au moins du cuivre, du fer, de l'aluminium, et de l'argent, de type Zr-Cu-Fe-Al-X, avec X étant au moins un élément de la famille Ti, Hf, V, Nb, Y, Cr, Mo, Fe, Co, Sn, Zn, P, Pd, Ag, Au, Pt, est connue par le document WO2006026882 relatif à l'alliage Zr33-81Cu6-45(Fe,Co)3-15Al5-21-X0-6.A family of zirconium-based alloys comprising at least copper, iron, aluminum, and silver, of the Zr-Cu-Fe-Al-Ag type is known from the document. "MSEA, Vol 527 (2010) 1444-1447" , which studies the influence of Fe on the thermophysical properties of the alloy (Zr 46 Cu 39.2 Ag 7.8 Al 7 ) 100-y Fe y with 0 <y <7. The Cu / Zr ratio is high, and therefore the corrosion resistance is not good. A family of zirconium alloys comprising at least copper, iron, aluminum, and silver, of the Zr-Cu-Fe-Al-X type, with X being at least one element of the family Ti, Hf, V, Nb, Y, Cr, Mo, Fe, Co, Sn, Zn, P, Pd, Ag, Au, Pt, is known from the document WO2006026882 relating to the alloy Zr 33-81 Cu 6-45 (Fe, Co) 3-15 Al 5-21 -X 0-6 .

La même famille est encore connue par le document CN102534439 , qui concerne plus particulièrement l'alliage Zr60-70Ti1-2.5Nb0-2.5Cu5-15Fe5-15Ag0-10Pd0-10Al7.5-12.5.The same family is still known from the document CN102534439 , which relates more particularly to the alloy Zr 60-70 Ti 1-2.5 Nb 0-2.5 Cu 5-15 Fe 5-15 Ag 0-10 Pd 0-10 Al 7.5-12.5 .

Au vu des limitations mentionnées dans ces différentes divulgations de la littérature, la mise au point de l'invention a nécessité une importante campagne d'essais pour améliorer les propriétés, et notamment le diamètre critique, des alliages amorphes sans nickel, et sans béryllium et sans nickel.In view of the limitations mentioned in these various disclosures of the literature, the development of the invention required a large test campaign to improve the properties, and in particular the critical diameter, of amorphous alloys without nickel, and without beryllium and nickel free.

Malgré les enseignements - a priori rédhibitoires - relatifs aux alliages de type Zr-Cu-Fe-Al-Ag, ou de type Zr-Cu-Fe-Al-X, qui ne sont pas compatibles avec le cahier des charges et notamment en ce qui concerne la résistance à la corrosion, qui doit être parfaite pour des composants d'habillage d'horlogerie, la démarche inventive a cherché à établir si le rôle particulier joué par le fer, avec son influence favorable sur les propriétés thermophysiques de l'alliage, pourrait servir de base à la définition de compositions particulières d'alliages avec un diamètre critique Dc* de préférence supérieur ou égal à 9 mm, et présentant une très bonne résistance à la corrosion, et une excellente stabilité de coloris dans le temps.Despite the lessons - a priori prohibitive - relating to alloys of the Zr-Cu-Fe-Al-Ag type, or of the Zr-Cu-Fe-Al-X type, which are not compatible with the specifications and in particular as regards which concerns the resistance to corrosion, which must be perfect for watch cladding components, the inventive approach sought to establish whether the particular role played by iron, with its favorable influence on the thermophysical properties of the alloy , could serve as a basis for the definition of particular compositions of alloys with a critical diameter D c * preferably greater than or equal to 9 mm, and having a very good resistance to corrosion, and excellent color stability over time.

A cette fin, l'invention ne comporte que des alliages comportant au moins 0.5% de fer.To this end, the invention comprises only alloys comprising at least 0.5% iron.

En effet, le système Zr-Cu-Fe-Al est choisi comme point de départ, car la littérature enseigne que ce système a une aptitude à la vitrification (GFA, glass-forming ability) relativement grande (plus grande que pour les alliages ternaires Zr-Cu-AI).Indeed, the Zr-Cu-Fe-Al system is chosen as a starting point, because the literature teaches that this system has a relatively high vitrification ability (GFA, glass-forming ability) (greater than for ternary alloys Zr-Cu-AI).

Principalement, le fer a été choisi pour les raisons suivantes :

  • le fait d'avoir 4 éléments (Zr-Cu-Al + Fe) augmente la complexité de l'alliage (il est plus difficile de former une structure ordonnée), et donc augmente son GFA ;
  • généralement, les meilleures compositions se trouvent autour des eutectiques profonds dans le diagramme des phases. Il est connu que le fer forme un eutectique profond avec le Zr, et des calculs thermodynamiques ont montré que le fer abaisse le liquidus dans le système quaternaire. Des eutectiques profonds se situent près de Zr60Cu25Fe5Al10 et Zr62.5Cu22.5Fe5Al10;
  • de plus, pour augmenter le GFA, l'énergie de mélange entre les principaux éléments doit être négative (ce qui est le cas pour Zr-Fe et Al-Fe).
Mainly, the iron was chosen for the following reasons:
  • having 4 elements (Zr-Cu-Al + Fe) increases the complexity of the alloy (it is more difficult to form an ordered structure), and therefore increases its GFA;
  • generally, the best compositions are found around deep eutectics in the phase diagram. Iron is known to form a deep eutectic with Zr, and thermodynamic calculations have shown that iron lowers the liquidus in the quaternary system. Deep eutectics are found near Zr60Cu25Fe5Al10 and Zr62.5Cu22.5Fe5Al10;
  • moreover, to increase the GFA, the mixing energy between the main elements must be negative (which is the case for Zr-Fe and Al-Fe).

Pourtant, le diamètre critique des alliages quaternaires Zr-Cu-Fe-Al n'est pas encore suffisamment grand pour réaliser des pièces d'habillage massives, telles qu'une carrure ou similaire. L'objectif d'un diamètre critique Dc* voisin de 9 mm, ou supérieur à cette valeur, tient compte du fait que, du moins en haute horlogerie, l'épaisseur d'une carrure est typiquement voisine de 5mm.However, the critical diameter of the Zr-Cu-Fe-Al quaternary alloys is not yet large enough to produce massive cladding pieces, such as a middle part or the like. The objective with a critical diameter D c * close to 9 mm, or greater than this value, takes into account the fact that, at least in fine watchmaking, the thickness of a middle part is typically close to 5mm.

La stratégie d'expérimentation a consisté à rajouter, à un alliage quaternaire de départ, des éléments supplémentaires afin d'augmenter le diamètre critique en utilisant la démarche principale suivante :

  • 1. Définir une base constituée d'un alliage quaternaire de départ Zr-Cu-Fe-Al. Par exemple : Zr58Cu27Fe5Al10. Le zirconium peut être remplacé par du hafnium, ou par un mélange zirconium-hafnium
  • 2. Choisir au moins deux (ou davantage) éléments X, pris dans une famille comportant Ti, V, Nb, Y, Cr, Mo, Co, Sn, Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, et Hf quand la base n'en comporte pas, et Zr quand la base n'en comporte pas ; dans l'expression Xa, on désigne par « a » le pourcentage cumulé de tous les éléments de type X
  • 3. Si un élément X choisi est parmi (Ti, Nb, Ta) il remplace le Zr. En effet, les éléments (Ti, Nb, Ta) sont chimiquement plus proches du Zr, en raison de leur proximité dans le tableau périodique des éléments, et de la facilité de formation de solutions solides avec le Zr, et ils sont donc utilisés pour remplacer le Zr
  • 4. Si un élément X est parmi (Pd, Pt, Ag, Au, Ru, Rh, Ir, Os) et donc, de façon similaire, chimiquement plus proche du Cu, il remplace le Cu
  • 5. Figer une composition d'alliage ainsi obtenue. Par exemple: X1= Nb, et X2= Ag ; l'alliage choisi est Zr58-X1Nbx1Cu25-X2AgX2Fe5Al12
  • 6. Fabriquer des alliages avec différentes teneurs de X1 et X2. Par exemple X1 =2% et 3%, et X2= 3.5% et 4.5%
  • 7. Mesurer les propriétés et surtout le diamètre critique Dc* des alliages, et identifier la meilleure composition. Par exemple Zr56Nb2Cu22.5Ag4.5Fe5Al10.
The experimentation strategy consisted in adding additional elements to a starting quaternary alloy in order to increase the critical diameter using the following main approach:
  • 1. Define a base made of a starting quaternary alloy Zr-Cu-Fe-Al. For example: Zr 58 Cu 27 Fe 5 Al 10 . Zirconium can be replaced by hafnium, or by a zirconium-hafnium mixture
  • 2. Choose at least two (or more) elements X, taken from a family comprising Ti, V, Nb, Y, Cr, Mo, Co, Sn, Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, and Hf when the base does not have one, and Zr when the base does not have one; in the expression Xa, we denote by "a" the cumulative percentage of all elements of type X
  • 3. If an element X chosen is among (Ti, Nb, Ta) it replaces the Zr. Indeed, the elements (Ti, Nb, Ta) are chemically closer to Zr, because of their proximity in the periodic table of the elements, and the ease of formation of solid solutions with Zr, and they are therefore used for replace the Zr
  • 4. If an element X is among (Pd, Pt, Ag, Au, Ru, Rh, Ir, Os) and therefore, similarly, chemically closer to Cu, it replaces Cu
  • 5. Freeze an alloy composition thus obtained. For example: X1 = Nb, and X2 = Ag; the alloy chosen is Zr 58-X1 Nb x1 Cu 25-X2 Ag X2 Fe 5 Al 12
  • 6. Fabricate alloys with different contents of X1 and X2. For example X1 = 2% and 3%, and X2 = 3.5% and 4.5%
  • 7. Measure the properties and especially the critical diameter D c * of the alloys, and identify the best composition. For example Zr 56 Nb 2 Cu 22.5 Ag 4.5 Fe 5 Al 10 .

Pour chaque alliage expérimental, des charges d'environ 70g d'alliage ont été préparées dans un four à arc en utilisant des éléments purs, de pureté supérieure à 99.95%. Ce pré-alliage a été ensuite refondu dans une machine de coulée centrifuge, avec creuset en oxyde de silicium, sous atmosphère d'argon, et coulé dans un moule en cuivre sous forme d'un cône (épaisseur max. 11 mm, largeur 20mm, angle d'ouverture 6.3°). Une coupe métallographique a été préparée au milieu de chaque cône dans le sens de sa longueur pour mesurer le diamètre critique Dc*, qui correspond à l'épaisseur du cône où la zone cristalline commence, tel que visible en figure 1.For each experimental alloy, charges of approximately 70 g of alloy were prepared in an arc furnace using pure elements, of purity greater than 99.95%. This pre-alloy was then remelted in a centrifugal casting machine, with a silicon oxide crucible, under an argon atmosphere, and cast in a copper mold in the form of a cone (max. Thickness 11 mm, width 20mm , opening angle 6.3 °). A metallographic section has been prepared at middle of each cone in the direction of its length to measure the critical diameter D c *, which corresponds to the thickness of the cone where the crystalline zone begins, as visible in figure 1 .

Le tableau ci-dessous résume les essais réalisés dans un système Zr-Cu-Fe-Al-X, X étant au moins un élément de la famille Ti, Hf, V, Nb, Y, Cr, Mo, Fe, Co, Sn, Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os.The table below summarizes the tests carried out in a Zr-Cu-Fe-Al-X system, X being at least one element of the family Ti, Hf, V, Nb, Y, Cr, Mo, Fe, Co, Sn , Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os.

Les compositions 1 et 2 sont connues, ne comportent pas de composant additionnel X, et correspondent aux enseignements du document WO2006026882 .The compositions 1 and 2 are known, do not comprise any additional component X, and correspond to the teachings of the document WO2006026882 .

Les compositions 3 et 4 concernent des compositions non divulguées dans la littérature, elles sont toutefois couvertes par certaines plages divulguées par le document WO2006026882 . La composition 3 comporte un composant X additionnel unique qui est l'argent, le diamètre critique est meilleur que celui des compositions 1 et 2, mais insuffisant pour satisfaire au cahier des charges de l'invention. La composition 4 comporte deux composants X additionnels, le niobium et l'argent, avec un % total de 6, et le diamètre critique est du même ordre que celui de l'échantillon 3.Compositions 3 and 4 relate to compositions which have not been disclosed in the literature, however, they are covered by certain ranges disclosed by the document. WO2006026882 . Composition 3 comprises a unique additional component X which is silver, the critical diameter is better than that of compositions 1 and 2, but insufficient to satisfy the specifications of the invention. Composition 4 has two additional X components, niobium and silver, with a total% of 6, and the critical diameter is of the same order as that of sample 3.

La campagne d'essais montre que le seul moyen d'augmenter sensiblement le diamètre critique Dc* est d'avoir dans l'alliage au moins deux composants X, et avec un % supérieur ou égal à 6,3.The test campaign shows that the only way to significantly increase the critical diameter D c * is to have at least two components X in the alloy, and with a% greater than or equal to 6.3.

Les compositions 5-12 sont entièrement nouvelles, et ne recoupent pas les plages de l'art antérieur. Parmi elles, les compositions 5 à 11 ont un diamètre critique Dc* supérieur ou égal à 9,5 mm. La composition 12 montre qu'un pourcentage cumulé « a » des composants X supérieur à une certaine valeur, en l'occurrence 10% en pourcentage atomique, n'apporte pas d'effet bénéfique, au contraire même, puisque le diamètre critique Dc* est sensiblement plus faible que les précédents.The compositions 5-12 are entirely new, and do not overlap with the ranges of the prior art. Among them, compositions 5 to 11 have a critical diameter D c * greater than or equal to 9.5 mm. Composition 12 shows that a cumulative percentage “a” of the components X greater than a certain value, in this case 10% in atomic percentage, does not bring any beneficial effect, on the contrary even, since the critical diameter D c * is significantly lower than the previous ones.

Les résultats montrent que le rajout d'éléments X augmente le diamètre critique Dc* et qu'idéalement il faut rajouter au moins deux éléments X pour maximiser leur effet. Les essais montrent que le diamètre critique Dc* est maximal quand le pourcentage cumulé « a » des éléments X se situe entre 6 et 10%.The results show that the addition of elements X increases the critical diameter D c * and that ideally it is necessary to add at least two elements X to maximize their effect. The tests show that the critical diameter D c * is maximum when the cumulative percentage "a" of the elements X is between 6 and 10%.

L'expérimentation prouve, encore, que l'ajout de terres rares, en petite quantité, est favorable pour amortir l'effet négatif de l'oxygène présent dans l'alliage (« oxygen scavenger »). N° Composition (en % atomique) Dc* (mm) % cumulé de X 1 Zr58Cu22Fe8Al10 5.0 0 2 Zr62.5Cu22.5Fe5Al10 6.1 0 3 (Zr58Cu22Fe8Al10)0.95Ag5 7.1 5 4 Zr56Nb2Cu21Ag4Fe5Al12 7.0 6 5 Zr55.9Nb2.1Cu22.8Ag2.1Pd2.1Fe4Al11 9.6 6.3 6 Zr56Ti2Cu22.5Ag4.5Fe5Al10 10.5 6.5 7 Zr56Nb2Cu22.5Ag4.5Fe5Al10 10.5 6.5 8 Zr56Cu22.5Ag4.5Pd2Fe5Al10 9.5 6.5 9 Zr57.5Nb20.5Cu21Ag4.5Fe4.5Al10 10 7 10 Zr56Nb2Cu21.5Ag5.5Fe5Al10 10 7.5 11 Zr55Nb2Cu21.5Ag4.5Pd2Fe5Al10 10 8.5 12 Zr57.5Nb3.5Cu20Ag3.5Pd2Fe3Al10.5 6.6 9 Experimentation proves, again, that the addition of rare earths, in small quantities, is favorable to dampen the negative effect of the oxygen present in the alloy ("oxygen scavenger"). No. Composition (in atomic%) D c * (mm) cumulative% of X 1 Zr58Cu22Fe8Al10 5.0 0 2 Zr62.5Cu22.5Fe5Al10 6.1 0 3 (Zr58Cu22Fe8Al10) 0.95Ag5 7.1 5 4 Zr56Nb2Cu21Ag4Fe5Al12 7.0 6 5 Zr55.9Nb2.1Cu22.8Ag2.1Pd2.1Fe4Al11 9.6 6.3 6 Zr56Ti2Cu22.5Ag4.5Fe5Al10 10.5 6.5 7 Zr56Nb2Cu22.5Ag4.5Fe5Al10 10.5 6.5 8 Zr56Cu22.5Ag4.5Pd2Fe5Al10 9.5 6.5 9 Zr57.5Nb20.5Cu21Ag4.5Fe4.5Al10 10 7 10 Zr56Nb2Cu21.5Ag5.5Fe5Al10 10 7.5 11 Zr55Nb2Cu21.5Ag4.5Pd2Fe5Al10 10 8.5 12 Zr57.5Nb3.5Cu20Ag3.5Pd2Fe3Al10.5 6.6 9

L'invention concerne ainsi un alliage amorphe massif, caractérisé en ce qu'il est exempt de nickel, et qu'il consiste, en valeurs en % atomique, en :

  • une base composée de zirconium ou/et hafnium, dont la teneur constitue la balance, avec un total zirconium et hafnium supérieur ou égal à 52.0, et inférieur ou égal à 62.0 ;
  • du cuivre: supérieur ou égal à 16.0, et inférieur ou égal à 28.0 ;
  • du fer: supérieur ou égal à 0.5, et inférieur ou égal à 10.0 ;
  • de l'aluminium: supérieur ou égal à 7.0, et inférieur ou égal à 13.0 ;
  • au moins un premier métal d'apport et un deuxième métal d'apport dits X pris dans la famille comportant Ti, V, Nb, Y, Cr, Mo, Co, Sn, Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, et Hf quand ladite base n'en comporte pas, et Zr quand ladite base n'en comporte pas, avec le pourcentage atomique cumulé « a » desdits au moins deux métaux d'apport étant supérieur ou égal à 6.0, et inférieur ou égal à 10.0.
The invention thus relates to a solid amorphous alloy, characterized in that it is free of nickel, and that it consists, in values in atomic%, of:
  • a base composed of zirconium and / or hafnium, the content of which constitutes the balance, with a total zirconium and hafnium greater than or equal to 52.0, and less than or equal to 62.0;
  • copper: greater than or equal to 16.0, and less than or equal to 28.0;
  • iron: greater than or equal to 0.5, and less than or equal to 10.0;
  • aluminum: greater than or equal to 7.0, and less than or equal to 13.0;
  • at least a first filler metal and a second filler metal called X taken from the family comprising Ti, V, Nb, Y, Cr, Mo, Co, Sn, Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, and Hf when said base does not, and Zr when said base does not, with the cumulative atomic percentage "a" of said at least two filler metals being greater or equal to 6.0, and less than or equal to 10.0.

Plus particulièrement, le premier métal d'apport et le deuxième métal d'apport sont pris dans la famille comportant Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, et Hf quand ladite base n'en comporte pas, et Zr quand ladite base n'en comporte pas, avec le pourcentage atomique cumulé de ces au moins deux métaux d'apport étant supérieur ou égal à 6.0, et inférieur ou égal à 10.0.More particularly, the first filler metal and the second filler metal are taken from the family comprising Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, and Hf when said base n 'does not, and Zr when said base does not, with the cumulative atomic percentage of these at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0.

Plus particulièrement encore, le premier métal d'apport et le deuxième métal d'apport sont pris dans la famille comportant Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, avec le pourcentage atomique cumulé de ces au moins deux métaux d'apport étant supérieur ou égal à 6.0, et inférieur ou égal à 10.0.More particularly still, the first filler metal and the second filler metal are taken from the family comprising Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, with the cumulative atomic percentage of these at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0.

Dans une variante particulière, l'alliage selon l'invention ne comporte que du zirconium et pas de hafnium.In a particular variant, the alloy according to the invention comprises only zirconium and no hafnium.

Dans une autre variante particulière, l'alliage selon l'invention ne comporte que du hafnium et pas de zirconium.In another particular variant, the alloy according to the invention comprises only hafnium and no zirconium.

De façon plus particulière, l'alliage selon l'invention est exempt de nickel et de béryllium.More particularly, the alloy according to the invention is free of nickel and beryllium.

Les meilleurs résultats jusqu'à présent ont été réalisés avec :

  • X = Ag+Nb;
  • X=Ag+Ti;
  • X = Nb+Ag+Pd.
The best results so far have been achieved with:
  • X = Ag + Nb;
  • X = Ag + Ti;
  • X = Nb + Ag + Pd.

De façon plus particulière encore, l'alliage selon l'invention est exempt de cobalt ou/et de chrome.Even more particularly, the alloy according to the invention is free of cobalt and / or chromium.

En somme, les alliages selon l'invention résistent à la corrosion, et ont une couleur stable (pas de ternissement ou décoloration au porté)In short, the alloys according to the invention resist corrosion, and have a stable color (no tarnishing or discoloration when worn)

L'invention concerne encore un composant 1 d'horlogerie ou de joaillerie réalisé en un tel alliage amorphe.The invention also relates to a component 1 of timepieces or jewelry made of such an amorphous alloy.

Plus particulièrement, le diamètre critique Dc* de l'alliage amorphe selon l'invention, qui constitue ce composant, est supérieur à 1.8 fois la plus forte épaisseur E de ce composant 1.More particularly, the critical diameter D c * of the amorphous alloy according to the invention, which constitutes this component, is greater than 1.8 times the greatest thickness E of this component 1.

L'invention concerne encore une montre 2 comportant au moins un tel composant 1 d'habillage.The invention also relates to a watch 2 comprising at least one such covering component 1.

Plus particulièrement, cette montre 2 comporte un tel composant 1 d'habillage qui est une carrure d'épaisseur maximale E comprise entre 4.0 et 5.0 mm réalisée dans un tel alliage amorphe présentant un diamètre critique Dc* supérieur à 8 mm.More particularly, this watch 2 comprises such a covering component 1 which is a middle part of maximum thickness E between 4.0 and 5.0 mm produced in such an amorphous alloy having a critical diameter D c * greater than 8 mm.

Claims (9)

  1. Bulk amorphous alloy, characterised in that it is nickel-free, and in that it consists, in at%, of:
    - a base made of zirconium and/or hafnium, the content whereof constitutes the balance, with a total zirconium and hafnium content of greater than or equal to 52.0, and less than or equal to 62.0;
    - copper: greater than or equal to 16.0, and less than or equal to 28.0;
    - iron: greater than or equal to 0.5, and less than or equal to 10.0;
    - aluminium: greater than or equal to 7.0, and less than or equal to 13.0;
    - at least one first so-called (X) filler metal and one second so-called (X) filler metal, selected from the family consisting of Ti, V, Nb, Y, Cr, Mo, Co, Sn, Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, and Hf when not included in said base, and Zrwhen not included in said base, with the cumulative atom percent of said at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0.
  2. Bulk amorphous alloy according to claim 1, characterised in that said first filler metal and said second filler metal are selected from the family consisting of Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, and Hf when not included in said base, and Zr when not included in said base, with the cumulative atom percent of said at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0.
  3. Bulk amorphous alloy according to claim 2, characterised in that said first filler metal and said second filler metal are selected from the family consisting of Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, and Os, with the cumulative atom percent of said at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0.
  4. Bulk amorphous alloy according to one of claims 1 to 3, characterised in that said alloy is nickel- and beryllium-free.
  5. Bulk amorphous alloy according to one of claims 1 to 4, characterised in that said alloy is cobalt- and/or chromium-free.
  6. Timepiece or jewellery component (1) made of an amorphous alloy according to one of claims 1 to 5.
  7. Component (1) according to claim 6, characterised in that the critical diameter (Dc*) of said amorphous alloy constituting said component (1) is greater than 1.8 times the largest thickness (E) of said component.
  8. Watch (2) including at least one said external component (1) according to claim 6 or 7.
  9. Watch (2) according to claim 8, characterised in that said watch (2) includes one said external component (1) which is a middle part of maximum thickness (E) that lies in the range 4.0 to 5.0 mm, made of an amorphous alloy according to one of claims 1 to 6, having a critical diameter (Dc*) greater than 8 mm.
EP15179473.2A 2015-08-03 2015-08-03 Bulk amorphous alloy made of nickel-free zirconium Active EP3128035B1 (en)

Priority Applications (4)

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EP15179473.2A EP3128035B1 (en) 2015-08-03 2015-08-03 Bulk amorphous alloy made of nickel-free zirconium
US15/188,588 US9933754B2 (en) 2015-08-03 2016-06-21 Nickel-free zirconium and/or hafnium-based bulk amorphous alloy
JP2016137321A JP6313821B2 (en) 2015-08-03 2016-07-12 Nickel-free zirconium and / or hafnium-based bulk amorphous alloys
CN201610608175.XA CN106399871B (en) 2015-08-03 2016-07-28 Nickel-free zirconium and/or hafnium-based bulk amorphous alloys

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9353428B2 (en) * 2012-03-29 2016-05-31 Washington State University Zirconium based bulk metallic glasses with hafnium
CN206372035U (en) * 2016-10-10 2017-08-04 东莞市坚野材料科技有限公司 The wearable device that amorphous alloy with antibacterial functions is made
CN106756647B (en) * 2016-12-12 2019-06-11 北京科技大学 A kind of high-ductility zirconium-based bulk amorphous alloy and preparation method thereof of the no beryllium without nickel
CN110479982B (en) * 2019-08-09 2021-07-30 飞亚达（集团）股份有限公司 Manufacturing method of watch appearance piece
CN111996470A (en) * 2020-08-26 2020-11-27 燕山大学 Zirconium-based bulk amorphous alloy and preparation method thereof
CN114606452B (en) * 2022-02-25 2022-12-06 中国科学院宁波材料技术与工程研究所 High-plasticity Hf-based two-phase amorphous alloy and preparation method thereof

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4126449A (en) * 1977-08-09 1978-11-21 Allied Chemical Corporation Zirconium-titanium alloys containing transition metal elements
WO1981000861A1 (en) * 1979-09-21 1981-04-02 Hitachi Metals Ltd Amorphous alloys
JPH07122120B2 (en) * 1989-11-17 1995-12-25 健 増本 Amorphous alloy with excellent workability
JP3359750B2 (en) * 1994-09-09 2002-12-24 明久 井上 Method for producing zirconium amorphous alloy rod and zirconium amorphous alloy cast by die
US5618359A (en) * 1995-02-08 1997-04-08 California Institute Of Technology Metallic glass alloys of Zr, Ti, Cu and Ni
US5735975A (en) * 1996-02-21 1998-04-07 California Institute Of Technology Quinary metallic glass alloys
US5772803A (en) * 1996-08-26 1998-06-30 Amorphous Technologies International Torsionally reacting spring made of a bulk-solidifying amorphous metallic alloy
US5797443A (en) * 1996-09-30 1998-08-25 Amorphous Technologies International Method of casting articles of a bulk-solidifying amorphous alloy
AU2001261172A1 (en) 2000-05-03 2001-11-12 California Institute Of Technology Fractional variation to improve bulk metallic glass forming capability
US6562156B2 (en) * 2001-08-02 2003-05-13 Ut-Battelle, Llc Economic manufacturing of bulk metallic glass compositions by microalloying
CA2458516A1 (en) * 2001-08-30 2003-03-27 Leibniz-Institut Fuer Festkoerper-Und Werkstoffforschung Dresden E.V. High-strength beryllium-free moulded body made from zirconium alloys which may be plastically deformed at room temperature
US6682611B2 (en) * 2001-10-30 2004-01-27 Liquid Metal Technologies, Inc. Formation of Zr-based bulk metallic glasses from low purity materials by yttrium addition
US6805758B2 (en) 2002-05-22 2004-10-19 Howmet Research Corporation Yttrium modified amorphous alloy
JP2004089580A (en) * 2002-09-03 2004-03-25 Kozo Nakamura Biomaterial member
US6896750B2 (en) * 2002-10-31 2005-05-24 Howmet Corporation Tantalum modified amorphous alloy
JP2006002238A (en) * 2004-06-21 2006-01-05 Ykk Corp Roll mold and method for manufacturing the same
EP1632584A1 (en) * 2004-09-06 2006-03-08 Eidgenössische Technische Hochschule Zürich Amorphous alloys on the base of Zr and their use
KR20110055399A (en) * 2009-11-19 2011-05-25 한국생산기술연구원 Sputtering target mother material of multi-component alloy system and method for manufacturing complex-coating thin film of multi-function
US20130032252A1 (en) 2011-08-04 2013-02-07 Institute Of Metal Research Chinese Academy Of Science Amorphous nickel-free zirconium alloy
EP2597166B1 (en) 2011-11-24 2014-10-15 Universität des Saarlandes Bulk metallic glass forming alloy
CN102534439B (en) 2012-02-12 2014-07-30 北京航空航天大学 Nickel-free low-copper zirconium-based bulk amorphous alloy and preparation method thereof
US9334553B2 (en) * 2012-03-29 2016-05-10 Washington State University Zirconium based bulk metallic glasses
US9963769B2 (en) * 2012-07-05 2018-05-08 Apple Inc. Selective crystallization of bulk amorphous alloy
EP2881488B1 (en) * 2013-12-06 2017-04-19 The Swatch Group Research and Development Ltd. Bulk amorphous alloy made of beryllium-free zirconium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

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JP2017031504A (en) 2017-02-09
US9933754B2 (en) 2018-04-03
US20170038733A1 (en) 2017-02-09
JP6313821B2 (en) 2018-04-18
CN106399871A (en) 2017-02-15
CN106399871B (en) 2021-03-23

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