Zirconium-based and beryllium free solid amorphous alloy

Abstract

The invention concerns a zirconium and/or hafnium based, beryllium free, solid, amorphous alloy, with the addition of silver and/or gold and/or platinum to increase its critical diameter.

Claims

1. A beryllium-free solid amorphous alloy, consisting of, in atomic percentage: zirconium and/or hafnium as at least one base metal, wherein a total content of said at least one base metal ranges from a minimum value of 50% to a maximum value of 63%; at least one first additional metal, wherein a total content of said at least one first additional metal ranges from a minimum value of 0% to a maximum value of 0.5%, said at least a first additional metal is selected from the group consisting of niobium and tantalum, and a content of niobium is less than or equal to 0.5%; at least one second additional metal, wherein a total content of said at least one second additional metal ranges from a minimum value of 1.2% to a maximum value of 4.5%, said at least one second additional metal is selected from the group consisting of, gold and platinum; at least one third additional metal, wherein a total content of said at least one third additional metal ranges from a minimum value of 8.5% to a maximum value of 17.5%, said at least one third additional metal is selected from the group consisting of nickel, cobalt, manganese, and iron; aluminium ranging from a minimum value of 9% to a maximum value of 13%; copper ranging from a minimum of value of 10% to a maximum value of 17.5%; and inevitable impurities, wherein the alloy has T.sub.x as calculated below of 98 K or less: T.sub.x=T.sub.xT.sub.g, where T.sub.xand T.sub.gis a crystallization point and a glass transition point of the alloy, respectively.

2. The alloy according to claim 1, wherein the total content of said at least one base metal ranges from a minimum value of 57% to a maximum value of 63%.

3. The alloy according to claim 1, wherein the total content of said at least one second additional metal in atomic percentage ranges from a minimum value of 1.2% to a maximum value of 4.0%.

4. The alloy according to claim 3, wherein the total content of said at least one second additional metal in atomic percentage ranges from a minimum value of 1.5% to a maximum value of 3.8%.

5. The alloy according to claim 4, wherein the total content of said at least one second additional metal in atomic percentage ranges from a minimum value of 2.6% to a maximum value of 3.0%.

6. The alloy according claim 1, wherein gold is present as the at least one second additional metal, and a content of gold in atomic percentage ranges from a minimum value of 1.5% to a maximum value of 2.5%.

7. The alloy according to claim 1, wherein platinum is present as the at least one second additional metal, and a content of platinum in atomic percentage ranges from a minimum value of 1.5% to a maximum value of 2.5%.

8. The alloy according to claim 1, wherein the total content of said at least one base metal is less than or equal to 60%.

9. The alloy according to claim 1, wherein a content of aluminium is more than 10.0%.

10. The alloy according to claim 1, wherein zirconium is present as the at least one base metal and a content ratio of zirconium to copper Zr/Cu ranges from a minimum value of 3.0 to a maximum value of 5.0.

11. The alloy according to claim 1, wherein zirconium is present as the at least one base metal and a content ratio of zirconium to copper and nickel in total Zr/(Cu+Ni) ranges from a minimum value of 1.5 to a maximum value of 3.0.

12. The alloy according to claim 1, wherein a content ratio of zirconium, hafnium, niobium, and tantalum in total to copper and nickel in total (Zr+Hf+Nb+Ta)/(Cu+Ni) ranges from a minimum value of 1.5 to a maximum value of 3.0.

13. The alloy according to claim 1, wherein said alloy does not contain niobium.

14. The alloy according to claim 1, wherein neither titanium nor niobium is present in said alloy.

15. The alloy according to claim 1, wherein the alloy includes less than 0.5% nickel in atomic percentage.

16. A timepiece or jewellery component, comprising the alloy according to claim 1.

17. A beryllium-free solid amorphous alloy, consisting of, in atomic percentage: zirconium and/or hafnium as at least one base metal, wherein a total content of said at least one base metal ranges from a minimum value of 50% to a maximum value of 63%; at least one first additional metal, wherein a total content of said at least one first additional metal ranges from a minimum value of 0% to a maximum value of 0.5%, said at least a first additional metal is selected from the group consisting of niobium and tantalum, and a content of niobium is less than or equal to 0.5%; at least one second additional metal, wherein a total content of said at least one second additional metal ranges from a minimum value of 1.2% to a maximum value of 4.5%, said at least one second additional metal is selected from the group consisting of, gold, palladium, and platinum; at least one third additional metal, wherein a total content of said at least one third additional metal ranges from a minimum value of8.5% to a maximum value of 17.5%, said at least one third additional metal is selected from the group consisting of chromium, cobalt, manganese, and iron; aluminium ranging from a minimum value of 9% to a maximum value of 13%; copper ranging from a minimum of value of 10% to a maximum value of 17.5%; and inevitable impurities, wherein the alloy has T.sub.x as calculated below of 98 K or less: T.sub.x =T.sub.x T.sub.gwhere T.sub.x and T.sub.g is a crystallization point and a glass transition point of the alloy, respectively.

18. The alloy according to claim 17, wherein the total content of said at least one base metal ranges from a minimum value of 57% to a maximum value of 63%.

19. The alloy according to claim 17, wherein gold is present as the at least one second additional metal, and a content of gold in atomic percentage ranges from a minimum value of 1.5% to a maximum value of 2.5%.

20. The alloy according to claim 17, wherein platinum is present as the at least one second additional metal, and a content of platinum in atomic percentage ranges from a minimum value of 1.5% to a maximum value of 2.5%.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Other features and advantages of the invention will appear upon reading the following detailed description, with reference to the annexed drawings, in which:

(2) FIG. 1 shows a schematic view of a critical diameter measurement in a conical sample;

(3) FIG. 2 shows a schematic view of a timepiece made of an alloy according to the invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

(4) The invention concerns the fields of horology and jewellery, in particular for the following structures: watch cases, case middles, main plates, bezels, push-buttons, crowns, buckles, bracelets, rings, earrings and others.

(5) The invention proposes to produce beryllium free amorphous steels, devised to have similar properties to those of amorphous alloys containing beryllium. Hereafter, an alloy containing no beryllium will be termed a beryllium free alloy and an alloy containing less than 0.5 atomic percent of nickel will be termed a nickel free alloy.

(6) Containing no beryllium means that the level of beryllium is preferably zero, or very low, the same as impurities, and preferably less than or equal to 0.1%.

(7) It is therefore sought to manufacture alloys, which include substitution elements for beryllium, and which have high values of critical diameter D.sub.c and gradient Tx.

(8) The invention further concerns a zirconium based, beryllium free, solid, amorphous alloy, with the addition of silver and/or gold and/or platinum to increase the critical diameter D.sub.c.

(9) More specifically, the invention concerns a solid amorphous alloy, characterized in that it contains no beryllium and in that it consists, in atomic percent values, of: a base composed of zirconium and/or hafnium, with the total zirconium and hafnium having a minimum value of 50% and a maximum value of 63%; a first additional metal, the total value of said at least a first additional metal or said first additional metals being comprised (minimum and maximum values included) between: a minimum value of 0.0% and maximum value of 0.5%, said at least a first additional metal being selected from a first group comprising niobium and tantalum, the niobium value being less than or equal to 0.5%; a second additional metal, the total value of said at least one second additional metal or said second additional metals being comprised (minimum and maximum values included) between: a minimum value of 1.2% and maximum value of 4.5%, said at least one second additional metal being selected from a second group comprising silver, gold and platinum; a third additional metal, the total value of said at least one third additional metal or said third additional metals being comprised (minimum and maximum values included) between: a minimum value of 8.5% and maximum value of 17.5%, said at least one third additional metal being selected from a third group comprising nickel, cobalt, manganese and iron; aluminium: minimum value 9%, maximum value 13%; copper and inevitable impurities: the complement to 100%, but less than or equal to 18%.

(10) More specifically, the base composed of zirconium and/or hafnium, has a total zirconium and hafnium content with a minimum value of 57% and a maximum value of 63%;

(11) Although numerous zirconium based amorphous compositions are known, the development of an amorphous alloy according to the composition of the invention produces an effect which is novel and extremely surprising, since in particular 2% of an additive is sufficient to significantly increase the critical diameter.

(12) The effect of the range 1.2% to 4.5% of the second additional metal chosen from a second group including silver, gold and platinum is clear: the addition to the alloy of one or the other, or of several, of these elements increases the critical diameter in comparison to an alloy that does not contain these additives, without decreasing the gradient Tx.

(13) A transition area showing a negative gradient of the critical diameter starts at around 4.5% and, beyond 5%, the critical diameter is significantly reduced with respect to the optimum quantity which is comprised (minimum and maximum values included) between the lower threshold of 1.2%, where the influence of the addition of the second additional metal starts to be seen, and the upper threshold of 4.5%.

(14) The range from 1.2% to 4.0% is favourable, and very good results have been obtained in the range from 1.5% to 3.8% and more particularly still in proximity to 2.8% in the range from 2.6% to 3.0%.

(15) More specifically, the gold content is between 1.5% and 2.5%.

(16) More specifically, the platinum content is between 1.5% and 2.5%.

(17) More specifically, the silver content is between 1.0% and 3.8%.

(18) In a specific embodiment, the total zirconium and hafnium content in the base is limited to 60%.

(19) In a specific variant, the alloy according to the invention does not contain titanium.

(20) In a specific variant, the alloy according to the invention does not contain niobium.

(21) In a specific variant, the alloy according to the invention does not contain either titanium or niobium.

(22) Palladium did not demonstrate any positive effect during the development of the invention, unlike the metals of the second group: silver, gold and platinum. It is possible to include palladium in this second group, but its content should preferably remain very low, in particular less than or equal to 1.0%.

(23) A non-limiting example embodiment is described hereafter: alloy charges of around 70 g are prepared in an arc furnace using pure elements (purity of more than 99.95%). The pre-alloy thereby obtained is then melted again in a centrifugal casting machine and cast in a copper mould in the shape of a cone (maximum thickness 11 mm, width 20 mm, opening angle 6.3).

(24) A DSC measurement is made of the vitreous transition and crystallisation temperature on samples taken from the end of each cone. A metallographic cut is made in the middle of each cone lengthways to measure the critical diameter D.sub.c*, wherein D.sub.c* is the thickness of the cone at the place where the crystalline area starts, as seen in FIG. 1.

(25) The following table summarises the test carried out (the compositions in italics are compositions known in the literature). It can be seen that with the proper quantity of silver, gold or platinum additive, the critical diameter Dc* can be increased significantly in comparison to basic alloys which do not contain these additives. Further, these additives do not decrease the gradient t.sub.x.

(26) TABLE-US-00001 Alloy T.sub.g T.sub.x T.sub.x D.sub.c* Zr65Cu15Ni10Al10 374 478 104 4.9 Zr65Cu13Ag2Ni10Al10 371 471 100 5.5 Zr65Cu11.5Ag3.Ni10Al10 383 453 70 4.2 Zr65Cu10Ag5Ni10Al10 375 439 64 5.2 Zr63Cu15Ag2Ni10Al10 380 496 116 5.8 Zr62Cu15Ag3Ni10Al10 388 504 116 8.6 Zr61Ti2Nb2Cu17.5Ni10Al7.5 378 447 69 8.5 Zr61Cu17.5Ag4Ni10Al7.5 382 490 108 6.8 Zr58.5Cu15.6Ni12.8Al10.3Nb2.8 409 497 88 5.7 Zr59.1Cu15.75Ni12.95Al10.40Ag1.8 398 502 104 4.9 Zr58.5Cu15.6Ni12.8Al10.3Ag2.8 400 498 98 8.6 Zr57.9Cu15.44Ni12.67Al10.19Ag3.8 394 503 109 8.1 Zr58.5Cu15.6Ni12.8Al10.3Pd2.8 409 507 98 5.1 Zr52.5Ti5Cu17.9Ni14.6Al10 404 459 55 6.8 Zr52.5Ti2.5Cu17.9Ni14.6Al12.5 420 510 90 6.3 Zr52.5Ti3.4Cu17.9Ni14.6Al11.6 418 501 83 6.6 Zr52.5Ti2.5Cu15.9Ag2Ni14.6Al12.5 422 514 92 >11 Zr52.5Ti2.5Cu15.9Au2Ni14.6Al12.5 426 512 86 >11 Zr52.5Ti2.5Cu15.9Pt2Ni14.6Al12.5 430 494 64 9.0 Zr52.5Ti2.5Cu15.9Ni14.6Pd2Al12.5 412 488 76 5.2 Zr52.5Ti2.5Cu17.9Ni12.6Pd2Al12.5 423 496 73 6.9 Zr52.5Ti2.5Cu16.9Ag1Ni14.6Al12.5 423 512 89 >11 Zr52.5Ti2.5Cu14.9Ag3Ni14.6Al12.5 418 508 90 >11 Zr52.5Nb2.5Cu15.9Ag2Ni14.6Al12.5 438 523 85 >11

(27) More specifically, the following alloys have given particularly satisfactory results: Zr62Cu15Ag3Ni10Al.sub.10, Zr58.5Cu 15.6Ni 12.8A110.3Ag2.8, Zr57.9Cu15.44Ni12.67A110.9Ag3.8 Zr52.5Ti2.5Cu15.9Ag2Ni14.6Al12.5 Zr52.5Ti2.5Cu15.9Au2Ni14.6Al12.5 Zr52.5T12.5Cu15.9Pt2Ni14.6Al12.5 Zr52.5T12.5Cu16.9Ag1Ni14.6Al12.5 Zr52.5T12.5Cu14.9Ag3Ni14.6Al12.5 Zr52.5Nb2.5Cu15.9Ag2Ni14.6Al12.5

(28) A first favourable sub-family concerns a total zirconium and hafnium content of more than 57.0%, with a total first additional metal content of less than or equal to 0.5%.

(29) A second favourable sub-family concerns a total zirconium and hafnium content of less than or equal to 53.0%, with a total first additional metal content of between 2.0% and 3.0%.

(30) In other variants of the invention, other elements, such as iron and manganese, are incorporated.

(31) The search for a compromise makes it possible to identify the best composition, in particular with an ideal silver content, which is advantageous due its cost which is lower than or equal to that of gold and platinum, yet provides the required effects.

(32) To optimise the alloy, several rules were determined during experiments: Particularly favourable results were obtained with: a ratio of the content of zirconium to the content of copper: Zr/Cu, of between 3.0 and 5.0; a ratio of the content of zirconium to the total content of copper and nickel: Zr/(Cu+Ni) of between 1.5 and 3.0; a ratio of the total content of zirconium, hafnium, titanium, niobium and tantalum to the total content of copper and nickel: (Zr,Hf,Ti,Nb,Ta)/(Cu+Ni) of between 1.5 and 3.0; the total value of said at least one first additional metal or said first additional metals (minimum and maximum values included) of between: a minimum value of 2.5% and a maximum value of 4.5%; an aluminium content of more than 10.0%.

(33) The question of incorporating nickel in the alloy arises because of the allergenic effects of nickel taken on its own or in an alloy composition containing certain other metals. However, the presence of nickel in an amorphous alloy is favourable for obtaining zirconium based amorphous alloys with high critical diameters and good anti-corrosion properties. By analogy, stainless steels also contain a high nickel content, and are widely used in jewellery and horology.

(34) The important constraint to be observed is that the alloy obtained satisfies the nickel release test in conformity with EN1811.

(35) In a particular variant of the invention, the alloy includes less than 0.5% nickel.

(36) It is understood that it is not sufficient simply to replace nickel with another metal to obtain the equivalent characteristics. The elements having a close atomic radius are iron, cobalt, palladium, manganese and chromium. This therefore means rethinking the entire composition of the amorphous alloy.

(37) Thus, the invention concerns a second solid amorphous alloy, characterized in that it contains no beryllium and in that it consists, in atomic percent values, of: a base composed of zirconium and/or hafnium, with the total zirconium and hafnium having a minimum value of 50% and a maximum value of 63%; a first additional metal, the total value of said at least a first additional metal or said first additional metals being comprised (minimum and maximum values included) between: a minimum value of 0% and maximum value of 0.5%, said at least a first additional metal being selected from a first group comprising niobium and tantalum, the niobium value being less than or equal to 0.5%; a second additional metal, the total value of said at least one second additional metal or said second additional metals being comprised (minimum and maximum values included) between: a minimum value of 1.2% and maximum value of 4.5%, said at least one second additional metal being selected from a second group comprising silver, gold, palladium and platinum; a third additional metal, the total value of said at least one third additional metal or said third additional metals being comprised (minimum and maximum values included) between: a minimum value of 8.5% and maximum value of 17.5%, said at least one third additional metal being selected from a third group comprising chromium, cobalt, manganese and iron; aluminium: minimum value 9%, maximum value 13%; copper and inevitable impurities: the complement to 100%, but less than or equal to 18%.

(38) More specifically, the base composed of zirconium and/or hafnium, has a total zirconium and hafnium content with a minimum value of 57% and a maximum value of 63%;

(39) More specifically, the gold content is between 1.5% and 2.5%.

(40) More specifically, the platinum content is between 1.5% and 2.5%.

(41) The invention also concerns a timepiece or jewellery component made of an alloy according to the invention, or a timepiece or piece of jewellery, particularly a watch, or a bracelet or suchlike.