EP3128035B1 - Massive amorphe legierung auf der basis von zirconium ohne nickel - Google Patents

Massive amorphe legierung auf der basis von zirconium ohne nickel 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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EP
European Patent Office
Prior art keywords
equal
nickel
amorphous alloy
alloys
zirconium
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EP15179473.2A
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English (en)
French (fr)
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EP3128035A1 (de
Inventor
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/de
Priority to US15/188,588 priority patent/US9933754B2/en
Priority to JP2016137321A priority patent/JP6313821B2/ja
Priority to CN201610608175.XA priority patent/CN106399871B/zh
Publication of EP3128035A1 publication Critical patent/EP3128035A1/de
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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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Adornments (AREA)

Claims (9)

  1. Massive amorphe Legierung, dadurch gekennzeichnet, dass sie frei von Nickel ist und, in Atomprozentwerten, besteht aus:
    - einer Basis, enthaltend Zirkonium und/oder Hafnium, wobei der Gehalt den Saldo bildet, mit einem Gesamtgehalt von Zirkonium und Hafnium größer oder gleich 52,0 und kleiner oder gleich 62,0;
    - Kupfer: größer oder gleich 16,0 und kleiner oder gleich 28,0;
    - Eisen: größer oder gleich 0,5 und kleiner oder gleich 10,0;
    - Aluminium: größer oder gleich 7,0 und kleiner oder gleich 13,0;
    - mindestens einem ersten Füllmetall und einem zweiten Füllmetall mit der Bezeichnung (X), die aus der Gruppe stammen, die Ti, V, Nb, Y, Cr, Mo, Co, Sn, Zn, P, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os umfasst, und, wenn die Basis dies nicht enthält, Hf, und, wenn die Basis dies nicht enthält, Zr, wobei der kumulierte Atomprozentsatz der mindestens zwei Füllmetalle größer oder gleich 6,0 und kleiner oder gleich 10,0 ist.
  2. Massive amorphe Legierung nach Anspruch 1, dadurch gekennzeichnet, dass das erste Füllmetall und das zweite Füllmetall aus der Gruppe stammen, die Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os umfasst, und, wenn die Basis dies nicht enthält, Hf, und, wenn die Basis dies nicht enthält, Zr, wobei der kumulierte Atomprozentsatz der mindestens zwei Füllmetalle größer oder gleich 6,0 und kleiner oder gleich 10,0 ist.
  3. Massive amorphe Legierung nach Anspruch 2, dadurch gekennzeichnet, dass das erste Füllmetall und das zweite Füllmetall aus der Gruppe stammen, die Ti, Nb, Pd, Ag, Au, Pt, Ta, Ru, Rh, Ir, Os umfasst, wobei der kumulierte Atomprozentsatz der mindestens zwei Füllmetalle größer oder gleich 6,0 und kleiner oder gleich 10,0 ist.
  4. Massive amorphe Legierung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Legierung frei von Nickel und Beryllium ist.
  5. Massive amorphe Legierung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Legierung frei von Kobalt und/oder Chrom ist.
  6. Bauteil (1) für Uhren oder Schmuck, hergestellt aus einer amorphen Legierung nach einem der Ansprüche 1 bis 5.
  7. Bauteil (1) nach Anspruch 6, dadurch gekennzeichnet, dass der kritische Durchmesser (Dc*) der amorphen Legierung, welche das Bauteil (1) bildet, größer ist als das 1,8-Fache der größten Dicke (E) des Bauteils.
  8. Tragbare Uhr (2), umfassend mindestens ein Ausstattungsbauteil (1) nach Anspruch 6 oder 7.
  9. Tragbare Uhr (2) nach Anspruch 8, dadurch gekennzeichnet, dass die tragbare Uhr (2) ein Verkleidungsbauteil (1) aufweist, welches ein Gehäusemittelteil mit einer maximalen Dicke (E) zwischen 4,0 und 5,0 mm ist, hergestellt aus einer amorphen Legierung nach einem der Ansprüche 1 bis 6 mit einem kritischen Durchmesser (Dc*) größer als 8 mm.
EP15179473.2A 2015-08-03 2015-08-03 Massive amorphe legierung auf der basis von zirconium ohne nickel Active EP3128035B1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP15179473.2A EP3128035B1 (de) 2015-08-03 2015-08-03 Massive amorphe legierung auf der basis von zirconium ohne nickel
US15/188,588 US9933754B2 (en) 2015-08-03 2016-06-21 Nickel-free zirconium and/or hafnium-based bulk amorphous alloy
JP2016137321A JP6313821B2 (ja) 2015-08-03 2016-07-12 ニッケル非含有ジルコニウム及び／又はハフニウム系バルク非晶質合金
CN201610608175.XA CN106399871B (zh) 2015-08-03 2016-07-28 无镍的锆和/或铪基块体非晶合金

Applications Claiming Priority (1)

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EP15179473.2A EP3128035B1 (de) 2015-08-03 2015-08-03 Massive amorphe legierung auf der basis von zirconium ohne nickel

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EP3128035B1 true EP3128035B1 (de) 2020-03-04

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EP (1) EP3128035B1 (de)
JP (1) JP6313821B2 (de)
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CN206372035U (zh) * 2016-10-10 2017-08-04 东莞市坚野材料科技有限公司 具有抗菌功能的非晶态合金制成的可穿戴设备
CN106756647B (zh) * 2016-12-12 2019-06-11 北京科技大学 一种无铍无镍的高塑性锆基块体非晶合金及其制备方法
CN110479982B (zh) * 2019-08-09 2021-07-30 飞亚达（集团）股份有限公司 手表外观件的制造方法
CN111996470A (zh) * 2020-08-26 2020-11-27 燕山大学 一种锆基大块非晶合金及其制备方法
CN114606452B (zh) * 2022-02-25 2022-12-06 中国科学院宁波材料技术与工程研究所 一种高塑性Hf基双相非晶合金及其制备方法

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Also Published As

Publication number Publication date
US20170038733A1 (en) 2017-02-09
CN106399871B (zh) 2021-03-23
EP3128035A1 (de) 2017-02-08
CN106399871A (zh) 2017-02-15
JP2017031504A (ja) 2017-02-09
US9933754B2 (en) 2018-04-03
JP6313821B2 (ja) 2018-04-18

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