EP3128035A1 - Bulk amorphous alloy made of nickel-free zirconium - Google Patents

Abstract

Solid amorphous alloy, nickel-free, consisting in atomic%, of: - a zirconium base and / or hafnium, constituting 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 two filler metals (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 has none, and Zr when said base has none, the cumulative atomic percentage of said filler metals being greater than or equal to 6.0, and less than or equal to 10.0.

Description

Field of the invention

The invention relates to a solid amorphous alloy.

The invention also relates to a watch 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 jewelery, in particular for structures: watch cases, squares, turntables, glasses, pushers, crowns, buckles, bracelets, rings, earrings and others.

Background of the invention

Amorphous alloys are increasingly used in watchmaking, jewelery, and jewelery, especially for structures: watch cases, casebacks, turntables, glasses, pushpieces, crowns, buckles, bracelets, and others.

The components for external use, intended to be in contact with the user's skin, must obey certain constraints, in particular because of the toxicity or allergenic effects of certain metals, in particular beryllium and nickel. Despite the particular intrinsic qualities of such metals, it is endeavored to place on the market, at least for the components likely to come into contact with the skin of the user, alloys with little or no beryllium or nickel .

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 . 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 D_c*, se trouvent dans les systèmes :
   • Zr-Ti-Cu-Ni-Be,
   • et Zr-Cu-Ni-Al.

Solid amorphous zirconium alloys have been known since the 1990s. The following publications concern such alloys:

1. [1] Zhang, et al., Amorphous Zr-Al-TM (TM = Co, Ni, Cu) Alloys with Significant Supercooled Liquid Region of Over 100K, 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 Glass 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 . The amorphous alloys with the best vitrification abilities, commonly referred to as GFA ("glass-forming ability"), and related to the critical diameter D _c *, are found in systems:
   • Zr-Ti-Cu-Ni-Be,
   • and Zr-Cu-Ni-Al.

• Zr44Ti11 Cu9.8Ni10.2Be25 (LM1 b)
• Zr65Cul7.5Ni10Al7.5 [1]
• Zr52.5Cu17.9Ni14.6A110Ti5 (Vit105) [2]
• Zr57Cu15.4Ni12.6Al10Nb5 (Vit106) et Zr58.5Cu15.6Ni12.8Al10.3Nb2.8 (Vit106a) [3]
• Zr61 Cu17.5Ni10A17.5Ti2Nb2 [4]

The compositions (in atomic%) of the most often used / characterized alloys are listed below:

• Zr44Ti11 Cu9.8Ni10.2Be25 (LM1b)
• Zr65Cul7.5Ni10Al7.5 [1]
• Zr52.5Cu17.9Ni14.6A110Ti5 (Vit105) [2]
• Zr57Cu15.4Ni12.6Al10Nb5 (Vit106) and Zr58.5Cu15.6Ni12.8Al10.3Nb2.8 (Vit106a) [3]
• Zr61 Cu17.5Ni10A17.5Ti2Nb2 [4]

Given the allergenic potential of nickel, these alloys are not usable for applications in contact with the skin, such as clothing parts or the like. In addition, because of the toxicity of beryllium the manufacture and machining of some of these alloys require special precautionary measures. This is unfortunate because these two elements stabilize the amorphous phase, and make it easier to obtain alloys having a critical diameter D _c * high. In addition, nickel has a positive effect on the corrosion resistance of zirconium-based amorphous alloys.

The nickel-free and beryllium-free zirconium-based amorphous alloys generally exhibit critical diameters that are lower than those of nickel and beryllium alloys, which is unfavorable for producing solid parts. It is therefore necessary to develop alloys such that the critical diameter D _c * is sufficiently important.

Summary of the invention

The invention proposes to produce solid amorphous alloys based on zirconium, or without nickel, or both nickel-free and beryllium-free, for horological applications.

The invention proposes to increase the critical diameter of at least nickel-free zirconium-based amorphous alloys, or both nickel-free and beryllium-free, while keeping a high value of ΔTx (difference between the crystallization temperature Tx and the glass transition temperature Tg).

The invention relates to a solid amorphous alloy based on zirconium and / or hafnium, free of nickel, with addition of other elements to increase its critical diameter, according to claim 1.

The invention also relates to a watch or jewelery component made of such an alloy.

Brief description of the drawings

• la figure 1 représente, de façon schématisée, la mesure du diamètre critique D_c* dans un échantillon conique ;
• la figure 2 représente, de façon schématisée, une pièce d'horlogerie réalisée en un alliage 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 represents, schematically, the measurement of the critical diameter D _c * in a conical sample;
• the figure 2 represents, schematically, a timepiece made of an alloy according to the invention.

Detailed Description of the Preferred Embodiments

The invention relates to the fields of watchmaking, jewelery, and jewelery, in particular for structures: watch cases, squares, turntables, glasses, pushers, crowns, buckles, bracelets, rings, earrings and others.

The invention proposes to make massive amorphous alloys based on nickel-free zirconium, or both nickel-free and beryllium-free, for horological applications, these alloys according to the invention being designed to have properties similar to those of alloys. amorphs containing nickel, or containing nickel and beryllium.

The invention proposes to increase the critical diameter of at least nickel-free zirconium-based amorphous alloys, or both nickel-free and beryllium-free, while keeping a high value of ΔTx.

By "free of Z" is meant that in the alloy, the content of Z is preferably zero, if not very low, as well as impurities, and preferably less than or equal to 0.1%.

The term "nickel-free alloy" will be referred to hereinafter as a nickel-free alloy, ie containing less than 0.1% in atomic%, of nickel, and "alloy without nickel and without beryllium", an alloy comprising less than 0.1 %, in atomic%, of nickel and comprising less than 0.1%, in atomic%, of beryllium.

It is therefore necessary to develop an alloy manufacturing, which include elements of substitution with nickel, or with both nickel and beryllium, which do not pose a problem in contact with the skin, alloys which have values of the critical diameter D _c * and the interval ΔTx.

Also the invention relates to a massive amorphous alloy based on zirconium, nickel free, with addition of some particular components to increase the critical diameter D _c *.

Indeed, the experiment conducted in the context of the present invention makes it possible to establish that the possibility of a good realization of a clockwork component, of a given thickness E, made 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.

Different families of nickel-free compositions are already known in the literature, but with low critical diameters and / or poor corrosion resistance.

A family of zirconium alloys comprising at least copper and aluminum, especially 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 of the critical diameter from 8mm to 12mm, by adding silver in 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 The corrosion resistance of this family of alloys is very poor and these compositions even have a tendency to discolor or darken with time at room temperature. The compositions do not contain iron.

A family of zirconium-based alloys comprising at least titanium, copper and aluminum, especially Zr-Ti-Cu-Al and Zr-Ti-Nb-Cu-Al, is known from the document US2013032252 . Zr _45-69 Ti _0.25 - ₈ Cu _21-35 Al _{7.5-15 alloys} and Zr _45-69 (Nb, Ti) _0.25-15 Cu _21-35 Al _7.5-13 with 0.25≤Ti≤8 _{alloys are} particularly known. . The compositions do not contain iron. The critical diameter disclosed is less than 10mm. It should be emphasized 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 around Zr60-62Ti2Cu24-28AI10-12. The comparison, carried out during the experimentation of the invention, according to the procedure described below, of a Zr61Ti2Cu26Al11 alloy supposed to have a critical diameter of 10 mm, made it possible to obtain only one critical diameter Dc * of 4.5mm. This gives rise to the greatest suspicion with regard to the very optimistic results displayed in certain documents of the prior art.

A family of zirconium alloys containing 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, so high price. The critical diameter is still 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 not very pure elements, for example with the use of industrial zirconium instead of pure zirconium. Therefore, 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 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. Attempts conducted in the context of the development of the invention have shown that these Zr-Nb-Cu-Pd-Al type compositions are not resistant to corrosion.

A family of zirconium 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 ratio Cu / Zr is high, and in fact 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 member of the Ti family , Hf, V, Nb, Y, Cr, Mo, Fe, Co, Sn, Zn, P, Pd, Ag, Au, Pt, is known from document WO2006026882 relating to the alloy Zr _33-81 Cu _6-45 (Fe, Co) _3-15 Al _5-21 -X _0-6 .

The same family is still known by 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 .

In view of the limitations mentioned in these various disclosures of the literature, the development of the invention required a major test campaign to improve the properties, and especially the critical diameter, of amorphous alloys without nickel, and without beryllium and nickel free.

Despite the teachings - a priori crippling - relating to Zr-Cu-Fe-Al-Ag type alloys, or Zr-Cu-Fe-Al-X type, which are not compatible with the specifications and in particular in this respect. As regards corrosion resistance, which must be perfect for clockwork components, the inventive step 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.

For this purpose, the invention comprises only alloys comprising at least 0.5% iron.

• 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).

Indeed, the Zr-Cu-Fe-Al system is chosen as a starting point, because the literature teaches that this system has a relatively large glass-forming ability (GFA) (greater than for ternary alloys). Zr-Cu-AI). Mainly, iron was chosen for the following reasons:

• the fact of having 4 elements (Zr-Cu-Al + Fe) increases the complexity of the alloy (it is more difficult to form an ordered structure), and thus increases its GFA;
• generally, the best compositions are around deep eutectics in the phase diagram. It is known that iron forms a deep eutectic with Zr, and thermodynamic calculations have shown that iron lowers the liquidus in the quaternary system. Deep eutectics are 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).

However, the critical diameter of Zr-Cu-Fe-Al quaternary alloys is not yet sufficiently large to produce massive covering parts, such as a middle part or the like. The objective of a critical diameter D _c * close to 9 mm, or greater than this value, takes into account the fact that, at least in Haute Horlogerie, the thickness of a caseband is typically close to 5mm.

• 1. Définir une base constituée d'un alliage quaternaire de départ Zr-Cu-Fe-AI. 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 Zr_58-X1Nb_X1Cu_25-X2Ag_X2Fe₅Al₁₂
• 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 D_c* des alliages, et identifier la meilleure composition. Par exemple Zr₅₆Nb₂Cu_22.5Ag_4.5Fe₅Al₁₀.

The experimental strategy consisted in adding, to a starting quaternary alloy, additional elements in order to increase the critical diameter by using the following main approach:

• 1. Define a base consisting 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 including Ti, V, Nb, Y, Cr, Mo, Co, Sn, Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os, and Hf when the base has none, and Zr when the base has none; in the expression Xa, we denote by "a" the cumulative percentage of all the 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 the Zr, because of their proximity in the periodic table of the elements, and the ease of formation of solid solutions with the Zr, and they are therefore used to replace the Zr
• 4. If an element X is among (Pd, Pt, Ag, Au, Ru, Rh, Ir, Os) and thus, similarly, chemically closer to Cu, it replaces Cu
• 5. Freeze an alloy composition thus obtained. For example: X1 = Nb, and X2 = Ag; the alloy selected is Zr _58-X1 Nb _X1 Cu _25-X2 Ag _X2 Fe ₅ Al ₁₂
• 6. Make alloys with different grades 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 * alloys, and identify the best composition. For example Zr ₅₆ Nb ₂ Cu _22.5 Ag _4.5 Fe ₅ Al ₁₀ .

For each experimental alloy, charges of about 70 g of alloy were prepared in an arc furnace using pure elements, purity greater than 99.95%. This pre-alloy was then re-melted in a centrifugal casting machine, with a silicon oxide crucible, under an argon atmosphere, and poured into a copper mold in the form of a cone (maximum thickness 11 mm, width 20 mm , opening angle 6.3 °). A metallographic section was prepared in the 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 .

The table below summarizes the tests carried out in a Zr-Cu-Fe-Al-X system, X being at least one element of the Ti, Hf, V, Nb, Y, Cr, Mo, Fe, Co, Sn family. , Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os.

The compositions 1 and 2 are known, do not comprise additional component X, and correspond to the teachings of the document WO2006026882 .

Compositions 3 and 4 relate to compositions that are not disclosed in the literature, but are nevertheless covered by certain ranges disclosed by the document WO2006026882 . Composition 3 comprises a single additional component X which is silver, the critical diameter is better than that of compositions 1 and 2, but insufficient to meet the specifications of the invention. Composition 4 comprises 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 increase substantially the critical diameter D _c * is to have in the alloy at least two components X, and with a% greater than or equal to 6.3.

Compositions 5-12 are entirely new, and do not intersect the ranges of the prior art. Among them, the compositions 5 to 11 have a critical diameter D _c * greater than or equal to 9.5 mm. The 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, since the critical diameter D _c * is substantially lower than the precedents.

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 experiment proves, again, that the addition of rare earths, in small quantity, is favorable to dampen the negative effect of the oxygen present in the alloy ("oxygen scavenger"). No. Composition (atomic%) D _c * (mm) Cumulated% of X 1 Zr58Cu22Fe8Al10 5.0 0 2 Zr62.5Cu22.5Fe5Al10 6.1 0 3 (Zr58Cu22Fe8Al10) 0.95Ag5 7.1 5 4 Zr56Nb2Cu21 Ag4Fe5Al12 7.0 6 5 Zr55.9Nb2.1 Cu22.8Ag2.1 Pd2.1 F e4Al11 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 Zr57.5Nb20.5Cu21 Ag4.5Fe4.5Al 10 10 7 10 Zr56Nb2Cu21.5Ag5.5Fe5Al10 10 7.5 11 Zr55Nb2Cu21.5Ag4.5Pd2Fe5Al1 0 10 8.5 12 Zr57.5Nb3.5Cu20Ag3.5Pd2Fe3A l10.5 6.6 9

• 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 nickel-free, 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 X in 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 has none, and Zr when said base has none, with the cumulative atomic percentage "a" of said at least two filler metals being greater than or equal to 6.0, and less than or equal to 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 and Zr when said base has none, 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.

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.

In a particular variant, the alloy according to the invention comprises only zirconium and no hafnium.

In another particular variant, the alloy according to the invention comprises only hafnium and no zirconium.

More particularly, the alloy according to the invention is free of nickel and beryllium.

• 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.

In an advantageous variant, the alloy further comprises between 0.1-1% of at least one rare earth, taken from a group comprising scandium, yttrium and lanthanides with atomic numbers of 57 to 71, the total of these rare earths greater than or equal to 0.01, and less than or equal to 1.0.

Among these rare earths, more particularly but not exclusively Sc, Y, Nd, Gd, are most often used.

More particularly, the alloy according to the invention is free of cobalt and / or chromium.

In short, the alloys according to the invention are resistant to corrosion and have a stable color (no tarnishing or discoloration on the surface)

The invention also relates to a watchmaking or jewelery component 1 made of such an amorphous alloy.

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.

The invention also relates to a watch 2 comprising at least one such dressing component 1.

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 made in such an amorphous alloy having a critical diameter D _c * greater than 8 mm.

Claims (10)

Solid amorphous alloy, characterized in that it is nickel-free, and consists, in atomic% values, 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 lower 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 one first filler metal and a second said filler metal (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 has none, and Zr when said base has none, with the cumulative atomic percentage of said at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0. Solid amorphous alloy according to claim 1, characterized in that said first filler metal and said 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 has none, and Zr when said base has none, with the cumulative atomic percentage of said at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0. Solid amorphous alloy according to claim 2, characterized in that said first filler metal and said 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 said at least two filler metals being greater than or equal to 6.0, and less than or equal to 10.0. Solid amorphous alloy according to one of claims 1 to 3, characterized in that said alloy comprises, in values in atomic%, at least one rare earth taken from a group comprising scandium, yttrium and lanthanides of atomic numbers of 57 to 71, the total of said rare earths being greater than or equal to 0.01, and less than or equal to 1.0. Solid amorphous alloy according to one of claims 1 to 4, characterized in that said alloy is free of nickel and beryllium. Solid amorphous alloy according to one of claims 1 to 5, characterized in that said alloy is free of cobalt and / or chromium. Component (1) for watches or jewelery made of an amorphous alloy according to one of claims 1 to 6. Component (1) according to the preceding claim, characterized in that the critical diameter (D _c *) of said amorphous alloy which constitutes said component (1) is greater than 1.8 times the greatest thickness (E) of said component Watch (2) comprising at least one said covering component (1) according to claim 7 or 8. Watch (2) according to claim 9, characterized in that said watch (2) comprises a said component (1) covering which is a middle of maximum thickness (E) between 4.0 and 5.0 mm made in an amorphous alloy according to one of claims 1 to 6 having a critical diameter (D _c *) greater than 8 mm.

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