EP3241078B1 - Timepiece or jewellery item made from lightweight precious alloy comprising titanium - Google Patents
Timepiece or jewellery item made from lightweight precious alloy comprising titanium Download PDFInfo
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- EP3241078B1 EP3241078B1 EP15810677.3A EP15810677A EP3241078B1 EP 3241078 B1 EP3241078 B1 EP 3241078B1 EP 15810677 A EP15810677 A EP 15810677A EP 3241078 B1 EP3241078 B1 EP 3241078B1
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- 229910045601 alloy Inorganic materials 0.000 title claims description 146
- 239000000956 alloy Substances 0.000 title claims description 146
- 239000010936 titanium Substances 0.000 title claims description 128
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 30
- 229910052719 titanium Inorganic materials 0.000 title claims description 29
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 164
- 239000010955 niobium Substances 0.000 claims description 66
- 239000011651 chromium Substances 0.000 claims description 55
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 229910052737 gold Inorganic materials 0.000 claims description 39
- 229910052763 palladium Inorganic materials 0.000 claims description 36
- 229910052758 niobium Inorganic materials 0.000 claims description 32
- 229910052804 chromium Inorganic materials 0.000 claims description 28
- 229910052697 platinum Inorganic materials 0.000 claims description 25
- 229910052720 vanadium Inorganic materials 0.000 claims description 25
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 229910052703 rhodium Inorganic materials 0.000 claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 230000000295 complement effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 129
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 95
- 239000010931 gold Substances 0.000 description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 33
- 229910052742 iron Inorganic materials 0.000 description 29
- 150000002739 metals Chemical class 0.000 description 24
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 21
- 229910052782 aluminium Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- 229910052709 silver Inorganic materials 0.000 description 16
- 239000010948 rhodium Substances 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 14
- 229910052718 tin Inorganic materials 0.000 description 14
- 229910052725 zinc Inorganic materials 0.000 description 14
- 239000011701 zinc Substances 0.000 description 14
- 229910052732 germanium Inorganic materials 0.000 description 13
- 229910052735 hafnium Inorganic materials 0.000 description 13
- 229910052750 molybdenum Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229910052726 zirconium Inorganic materials 0.000 description 13
- 229910052738 indium Inorganic materials 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 239000010944 silver (metal) Substances 0.000 description 11
- 229910052741 iridium Inorganic materials 0.000 description 10
- 239000010970 precious metal Substances 0.000 description 10
- 229910001258 titanium gold Inorganic materials 0.000 description 10
- 229910052721 tungsten Inorganic materials 0.000 description 10
- 229910052787 antimony Inorganic materials 0.000 description 9
- 229910052715 tantalum Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000003446 memory effect Effects 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 229910010380 TiNi Inorganic materials 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 5
- 241001080024 Telles Species 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 210000000540 fraction c Anatomy 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 3
- 229910017060 Fe Cr Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 241000897276 Termes Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 208000031968 Cadaver Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241001415961 Gaviidae Species 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010977 Ti—Pd Inorganic materials 0.000 description 1
- 208000030068 ZTTK syndrome Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/002—Metallic materials
- A44C27/003—Metallic alloys
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/02—Alloys based on gold
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B45/00—Time pieces of which the indicating means or cases provoke special effects, e.g. aesthetic effects
- G04B45/0076—Decoration of the case and of parts thereof, e.g. as a method of manufacture thereof
Definitions
- the invention relates to a watch trim element, taken from middle part, case back, bezel, bracelet, clasp, the material of which is a titratable alloy, which comprises at least titanium, palladium and niobium.
- the invention also relates to a timepiece or jewelry piece comprising at least one such trim component.
- the invention relates to the field of trim parts for watches, jewelry, or jewelry.
- a characteristic common to most of the precious alloys used in watchmaking is their relatively high density (> 10 g / cm 3 ). Indeed, the two main precious metals used in watchmaking, namely gold and platinum, have respective densities of approximately 19.3 and 21.5 g / cm 3 . This has the consequence of making their alloys relatively heavy. Silver and palladium are lighter (10.5 and 12 g / cm 3 respectively) but much less used in watchmaking.
- WO 2012/119647 A1 describes ceramic-precious metal composites capable of achieving relatively low densities ( ⁇ 8 g / cm 3 ).
- the equi-atomic Ti phases (Pd / Pt / Au). Indeed, these phases can be similar to the equi-atomic phase TiNi used in certain shape memory alloys.
- the equi-atomic phases TiPd, TiPt and TiAu have a certain ductility and can, under certain conditions, exhibit behaviors typical of those of TiNi shape memory alloys.
- the equi-atomic alloys TiPd, TiPt and TiAu have been known for a long time and have been the subject of several studies aimed at high temperature shape memory alloys.
- TiPd and TiAu alloys are titratable and therefore interesting for watchmaking and jewelry as particularly light precious metals.
- the document EP0267318 in the name of HAFNER cites certain palladium alloys: from 25 to 50% by mass of palladium, with 37 to 69% silver, and a complement among copper, zinc, gallium, cobalt, indium, tin, iron, aluminum, nickel, germanium, rhenium, but without titanium, and other alloys, from 51 to 95% palladium, with contributions of different metals, including one only alloy comprises gold, with by mass 70% palladium, 15% silver, 5% copper, 5% zinc, 3% platinum, 2% gold.
- the only composition disclosed with titanium, of the Ti 5 Pd 95 type relates to an alloy with 5% titanium and 95% palladium.
- the document EP0239747 in the name of SUMITOMO describes the addition of 0.001 to 20% of chromium to an alloy of the titanium-palladium type with 40 to 60 atomic% of titanium, the balance being made on the palladium.
- the disclosures relate to seven 50 atomic% titanium alloys, with 40 to 50 atomic% palladium, and 0 to 10 atomic% chromium: Ti 50 Pd 40 , Ti 50 Pd 45 Cr 5 , Ti 50 Pd 43 Cr 7 , Ti 50 Pd 42 Cr 8 , Ti 50 Pd 41.5 Cr 8.5 , Ti 50 Pd 41 Cr 9 , Ti 50 Pd 40 Cr 10 .
- the document CH704233 in the name of RICHEMONT describes the use in watchmaking of titanium alloys, of the Ti-10-2-3 type comprising vanadium, iron and aluminum, of the Ti13-11-3 type comprising vanadium, chromium and aluminum, of Ti-15-3 type comprising vanadium, chromium, aluminum, and tin, of Ti-5-5-5-3 type comprising aluminum, vanadium , molybdenum and chromium. These alloys contain neither palladium nor gold.
- the document GB876887A in the name of DEGUSSA describes a malleable gold alloy with high electrical resistance, intended for use as a material for electrical resistances, consisting of 3 to 8% iron, 1 to 5% titanium, the remainder being gold and inevitable impurities.
- up to 30% of the gold is replaced by silver. More specifically, up to 65% of the gold is replaced by palladium. More particularly, 50% of the gold is replaced by palladium.
- the alloy consists of 85 to 40% gold, 10 to 55% palladium, 1 to 5% titanium and 3 to 8% iron; more particularly, the sum of titanium and iron is less than 7% and the ratio between the two components is between 0 25-0 5: 1.
- the alloy consists of 60 to 70% gold, 1-3% titanium, up to 35% palladium and 3-5% iron.
- the document JP H06 145843A TOKIN CORP of May 27, 1994 relates to devices for detecting defective electronic parts.
- the invention proposes to produce timepiece trim elements, which are both valuable for benefiting from the title and resistance over time and against corrosion, and lighter than known alloys.
- the invention relates to a covering element for a timepiece or jewelry piece, according to claim 1.
- the invention also relates to a timepiece or jewelry piece comprising at least one such covering element.
- the invention relates to the replacement of gold and palladium in alloys comprising titanium.
- the invention relates to a cladding element 1 for watches or jewelry (including jewelry) made of a light precious alloy comprising titanium, and any timepiece or jewelry piece comprising such an element.
- the research which led to the invention relates to two families of alloys, described successively.
- the first family of alloys describes nine typical compositions (first to ninth), using five groups of metals (first to seventh) and some of their subgroups.
- alloys as described above in Table 1, which are overloaded with precious metal relative to the titles to which they can be stamped, generate an unnecessary additional cost.
- advantageous substitutes may be suitable for the precious metal overload, and in particular the metals of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo , Ta, W.
- the elements of a third group comprising: Cr, Mn, Cu, Zn and Ag, can be introduced in a limited quantity ( ⁇ 10% at.) In the TiPd and TiAu alloys to replace palladium and gold, respectively.
- the elements of a fourth group comprising: Al, Si, Ge, Sn, Sb and In, can be introduced in small quantities ( ⁇ 4% at.) In the TiPd and TiAu alloys, replacing titanium or palladium and gold, respectively.
- the substitute materials should not pose a health risk.
- substitute materials for the latter should not be valuable.
- the substitute materials in order not to not too heavy the alloy, the substitute materials, ideally, are not heavier than the substituted metal.
- a particularly advantageous implementation of the invention relates to the substitution of a part of the palladium in a TiPd alloy.
- the invention therefore relates to a ductile alloy based on the equi-atomic intermetallic Ti-Pd, in which the excess of palladium relative to the mass content of Pd500 is partially or totally replaced by a non-precious element, such that the titanium always represents 50 atomic% of the final alloy.
- a ductile alloy based on the equi-atomic intermetallic Ti-Pd, in which the excess of palladium relative to the mass content of Pd500 is partially or totally replaced by a non-precious element, such that the titanium always represents 50 atomic% of the final alloy.
- Such an alloy has sufficient ductility to provide formability similar to that of conventional titanium alloys.
- the ternary TiPdFe and TiPdNb alloys make it possible to achieve the desired titer.
- the TiPdNb alloys do not exhibit any parasitic shape memory effect, which is advantageous.
- composition of the alloy can be formulated according to one of the following compositions, where all the fractions are atomic:
- Composition according to the fifth composition and for which M comprises Fe and / or Nb as majority elements.
- composition according to the sixth composition and containing 50% by mass of palladium.
- the atomic composition Ti49.7Pd32Fe15.3Cr3 exhibits interesting characteristics: low memory effect, low amount of second phase, and not too high mechanical properties.
- compositions of this ninth composition atomically containing 12.5 and 10.5% niobium exhibit a shape memory effect while the composition Ti 50 Pd 35.5 Nb 14.5 of figure 1 containing 14.5% niobium does not exhibit such an effect.
- This composition, according to the invention, at 14.5% niobium makes it possible to overcome these effects thanks to its two-phase nature.
- the invention thus relates to a trim component for a timepiece or jewelry piece, made of a light precious alloy comprising titanium and niobium.
- the composition of this alloy obeys the atomic composition: Ti ax (Zr, Hf) x M y Pd 1-ay , with 0.3 ⁇ a ⁇ 0.6, 0 ⁇ x ⁇ 0.15, 0.01 ⁇ y ⁇ 0.4, and M being one or more from a first group composed of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al , Si, Ge, Sn, Sb, In.
- this similar alloy of the invention comprises between 15 and 60 atomic% of titanium, between 0 and 69 atomic% of palladium, between 1 and 40 atomic% of gold, and the complement to 100% atomic comprises a total of between 0 and 15 atomic% of zirconium and hafnium, and one or more components taken from a subgroup of the first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.
- the alloy contains in atomic% more palladium than gold.
- the alloy comprises between 30% and 60 atomic% of titanium, and the remainder of said alloy comprises a majority of palladium, and, in an amount greater than 10 atomic% of the total of the alloy, at least one metal from a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.
- the alloy comprises between 30% and 60 atomic% of titanium, and the remainder of this alloy contains a majority of gold, and, in an amount greater than 10 atomic% of the total of l 'alloy, at least one metal from a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.
- the alloy comprises at least one metal from a third group comprising: Cr, Mn, Cu, Zn and Ag, the overall quantity of metals from said third group is less than 10 atomic% of the total of the alloy.
- the alloy comprises at least one metal from a fourth group comprising: Al, Si, Ge, Sn, Sb and In, the overall quantity of metals from the fourth group is less than 4 Atomic% of the total alloy.
- the alloy contains between 49.0 and 51.0 atomic% of titanium.
- the total in atomic% of titanium, zirconium and hafnium is between 49.0 and 51.0 atomic%.
- the alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd 1-ay , with 0.3 ⁇ a ⁇ 0.6; 0 ⁇ x ⁇ 0.05; 0.01 ⁇ y ⁇ 0.4.
- the alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd z , with 0.3 ⁇ a ⁇ 0.6; 0 ⁇ x ⁇ 0.05; 0.01 ⁇ y ⁇ 0.4; 0.2 ⁇ z ⁇ 0.55.
- the alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd z , with 0.44 ⁇ a ⁇ 0.55; 0 ⁇ x ⁇ 0.05; 0.07 ⁇ y ⁇ 0.28; 0.25 ⁇ z ⁇ 0.45.
- M comprises one or more elements taken from a fifth group comprising: Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn , In.
- M comprises Fe and / or Nb as majority elements.
- the alloy comprises 50% by weight of palladium. This proportion by mass of the total of the alloy does not naturally come into contradiction with the atomic proportions of the alloying elements, this is an additional condition, in no way incompatible.
- the second family of alloys describes compositions, in particular using three groups of metals (main group of metals and two subgroups of metals) and five groups of traces (main group of traces and four subgroups of traces) . What follows concerns this second family.
- this alloy comprises, in atomic proportions of the total, less than 0.3% boron.
- the traces of metal T are taken from a first subgroup of traces comprising Nb, V, Mo, Ta, W, Fe, Ni, Ru, Rh, Ir, Cr, Mn, Cu, Zn, Ag, Al, B, Si, Ge, Sn, Sb, In, with the exception of the metals M incorporated in the alloy.
- the traces of metal T are taken from a second subgroup of traces comprising Nb, V, Fe, Ru, Rh, Au, Pt, Cr, B, to except for M metals incorporated in the alloy.
- Another similar alloy of the invention comprises a single trace of metal T constituted by chromium, the alloy obeying the atomic formulation Ti a Pd b Fe c Cr d .
- the level of palladium can advantageously be reduced to reduce the cost of the alloy.
- the mass content of palladium is less than or equal to 51.0% of the total of the alloy.
- the invention also relates to a timepiece 10 or jewelry piece, in particular a watch, comprising at least one such covering element 1.
- the various alloys selected above are ductile, and therefore allow shaping by the usual deformation methods.
- the selection of the alloys with substitution components according to the invention also makes it possible to eliminate the shape memory effect observed in most of the base alloys described.
- the Ti 0.5 Pd 0.354 Nb 0.146 alloy has an almost zero shape memory effect.
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Adornments (AREA)
- Materials For Medical Uses (AREA)
- Powder Metallurgy (AREA)
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Description
L'invention concerne un élément d'habillage de montre, pris parmi carrure, fond, lunette, bracelet, fermoir, dont le matériau est un alliage titrable, qui comporte au moins du titane, du palladium et du niobium.The invention relates to a watch trim element, taken from middle part, case back, bezel, bracelet, clasp, the material of which is a titratable alloy, which comprises at least titanium, palladium and niobium.
L'invention concerne encore une pièce d'horlogerie ou de bijouterie comportant au moins un tel composant d'habillage.The invention also relates to a timepiece or jewelry piece comprising at least one such trim component.
L'invention concerne le domaine des pièces d'habillage d'horlogerie, de bijouterie, ou de joaillerie.The invention relates to the field of trim parts for watches, jewelry, or jewelry.
Une caractéristique commune à la plupart des alliages précieux utilisés en horlogerie est leur masse volumique relativement élevée (> 10 g/cm3). En effet, les deux principaux métaux précieux utilisés en horlogerie, à savoir l'or et le platine, ont des masses volumiques respectives d'environ 19.3 et 21.5 g/cm3. Ceci a pour conséquence de rendre leurs alliages relativement lourds. L'argent et le palladium sont plus légers (10.5 et 12 g/cm3 respectivement) mais beaucoup moins utilisés dans l'horlogerie.A characteristic common to most of the precious alloys used in watchmaking is their relatively high density (> 10 g / cm 3 ). Indeed, the two main precious metals used in watchmaking, namely gold and platinum, have respective densities of approximately 19.3 and 21.5 g / cm 3 . This has the consequence of making their alloys relatively heavy. Silver and palladium are lighter (10.5 and 12 g / cm 3 respectively) but much less used in watchmaking.
D'autre part, l'utilisation de matériaux légers comme le titane et, dans une moindre mesure, l'aluminium, dans des éléments d'habillage horloger est relativement répandue de nos jours. Toutefois, à l'heure actuelle, peu d'alliages peuvent être considérés comme précieux (titrables) et légers à la fois.On the other hand, the use of light materials such as titanium and, to a lesser extent, aluminum, in watch trim elements is relatively widespread nowadays. However, at present, few alloys can be considered valuable (titratable) and light at the same time.
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La réalisation d'alliages de métaux légers et de métaux précieux ne permet généralement pas d'obtenir des matériaux ductiles, et aboutit dans la quasi-totalité des cas à des phases intermétalliques fragiles.The production of alloys of light metals and precious metals does not generally make it possible to obtain ductile materials, and in almost all cases results in fragile intermetallic phases.
Toutefois, une exception existe pour les phases équi-atomiques Ti(Pd/Pt/Au). En effet, ces phases peuvent s'apparenter à la phase équi-atomique TiNi utilisée dans certains alliages à mémoire de forme. De la même manière, les phases équi-atomiques TiPd, TiPt et TiAu possèdent une certaine ductilité et peuvent, sous certaines conditions, présenter des comportements typiques de ceux des alliages à mémoire de forme TiNi. Les alliages équi-atomiques TiPd, TiPt et TiAu sont connus de longue date et ont fait l'objet de plusieurs études visant les alliages à mémoire de forme à haute température.However, an exception exists for the equi-atomic Ti phases (Pd / Pt / Au). Indeed, these phases can be similar to the equi-atomic phase TiNi used in certain shape memory alloys. Likewise, the equi-atomic phases TiPd, TiPt and TiAu have a certain ductility and can, under certain conditions, exhibit behaviors typical of those of TiNi shape memory alloys. The equi-atomic alloys TiPd, TiPt and TiAu have been known for a long time and have been the subject of several studies aimed at high temperature shape memory alloys.
L'effet de l'ajout d'éléments d'addition autres que Ni, Pd, Pt, Au, dans ces systèmes a principalement été étudié pour les alliages TiNi. Les recherches portant sur les ajouts ternaires aux alliages TiPd, TiPt et TiAu sont sensiblement plus rares. On sait néanmoins que l'ajout de fer au système TiPd a une influence sur les transformations de phases du système.The effect of adding addition elements other than Ni, Pd, Pt, Au, in these systems has mainly been studied for TiNi alloys. Research on ternary additions to TiPd, TiPt and TiAu alloys is noticeably rarer. It is nevertheless known that the addition of iron to the TiPd system has an influence on the phase transformations of the system.
La majorité de la littérature portant sur les ajouts aux alliages binaires équi-atomiques TiNi, TiPd, TiPt et TiAu se concentre sur la modification des propriétés de mémoire de forme et des propriétés dites super-élastiques de ces alliages (amplitude, température de transition). Cependant, aucune étude ne concerne la problématique de l'utilisation de tels alliages en bijouterie/horlogerie et des contraintes y associées, à savoir la formabilité et le titre (pourcentage de métal précieux).Most of the literature on additions to equi-atomic binary alloys TiNi, TiPd, TiPt and TiAu focuses on modifying the shape memory properties and the so-called super-elastic properties of these alloys (amplitude, transition temperature) . However, no study concerns the problem of the use of such alloys in jewelry / watchmaking and the associated constraints, namely formability and titer (percentage of precious metal).
Les compositions massiques des phases équi-atomiques ductiles des alliages TiPd, TiPt et TiAu sont présentées dans le tableau 1, ci-dessous, qui établit la composition des phases équi-atomiques Ti-(Pd, Pt, Au) et la comparaison avec les titres légaux en vigueur en Suisse.
On remarque que les alliages TiPd et TiAu sont titrables et donc intéressants pour l'horlogerie et la bijouterie comme métaux précieux particulièrement légers.Note that TiPd and TiAu alloys are titratable and therefore interesting for watchmaking and jewelry as particularly light precious metals.
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D'autres enseignements concernent, pour d'autres applications que celles de l'invention, et principalement pour la fonctionnalité de mémoire de forme, des alliages comportant du titane.Other teachings relate, for applications other than those of the invention, and mainly for the shape memory functionality, to alloys comprising titanium.
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L'invention se propose de réaliser des éléments d'habillage d'horlogerie, à la fois précieux pour bénéficier du titre et de la tenue dans le temps et à la corrosion, et plus légers que les alliages connus.The invention proposes to produce timepiece trim elements, which are both valuable for benefiting from the title and resistance over time and against corrosion, and lighter than known alloys.
A cet effet, l'invention concerne un élément d'habillage pour pièce d'horlogerie ou de bijouterie, selon la revendication 1.To this end, the invention relates to a covering element for a timepiece or jewelry piece, according to claim 1.
L'invention concerne encore une pièce d'horlogerie ou de bijouterie comportant au moins un tel élément d'habillage.The invention also relates to a timepiece or jewelry piece comprising at least one such covering element.
D'autres caractéristiques et avantages de l'invention apparaîtront à la lecture de la description détaillée qui va suivre, en référence aux dessins annexés, où :
- la
figure 1 compare les courbes contrainte-déformation d'alliages testés en compression avec une vitesse de déformation de 0.001 /s :- ∘ en trait interrompu Ti50Pd35.5Nb14.5,
- ∘ en trait continu Ti50Pd32Fe18,
- ∘ en trait pointillé Ti44.5Pd35Nb11Fe9.5
- ∘ en trait mixte Ti50Pd50.
- la
figure 2 représente une montre comportant une boîte et un bracelet selon l'invention.
- the
figure 1 compares the stress-strain curves of alloys tested in compression with a strain rate of 0.001 / s:- ∘ in broken line Ti 50 Pd 35.5 Nb 14.5 ,
- ∘ continuous line Ti 50 Pd 32 Fe 18 ,
- ∘ in dotted line Ti 44.5 Pd 35 Nb 11 Fe 9.5
- ∘ dashed line Ti 50 Pd 50 .
- the
figure 2 shows a watch comprising a case and a bracelet according to the invention.
Toutes les concentrations exprimées dans la description ci-dessous sont atomiques, sauf mention contraire.All the concentrations expressed in the description below are atomic, unless otherwise stated.
L'invention s'intéresse au remplacement de l'or et du palladium dans des alliages comportant du titane.The invention relates to the replacement of gold and palladium in alloys comprising titanium.
L'invention concerne un élément d'habillage 1 d'horlogerie ou de bijouterie (incluant la joaillerie) en alliage précieux léger comportant du titane, et toute pièce d'horlogerie ou de bijouterie comportant un tel élément.The invention relates to a cladding element 1 for watches or jewelry (including jewelry) made of a light precious alloy comprising titanium, and any timepiece or jewelry piece comprising such an element.
Les recherches ayant abouti à l'invention concernent deux familles d'alliages, décrites successivement.The research which led to the invention relates to two families of alloys, described successively.
La première famille d'alliages décrit neuf compositions-type (première à neuvième), faisant appel à cinq groupes de métaux (premier à septième) et à certains de leurs sous-groupes.The first family of alloys describes nine typical compositions (first to ninth), using five groups of metals (first to seventh) and some of their subgroups.
L'utilisation d'alliages, tels que décrits plus haut dans le tableau 1, qui sont surchargés en métal précieux par rapport aux titres auxquels ils peuvent être poinçonnés, engendrent un surcoût inutile. Afin de résoudre ce problème, des substituts avantageux peuvent convenir pour la surcharge de métal précieux, et notamment les métaux d'un deuxième groupe comportant : Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.The use of alloys, as described above in Table 1, which are overloaded with precious metal relative to the titles to which they can be stamped, generate an unnecessary additional cost. In order to solve this problem, advantageous substitutes may be suitable for the precious metal overload, and in particular the metals of a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo , Ta, W.
Ces éléments peuvent être introduits en grande quantité (>10% atomique) dans les alliages TiPd et TiAu en remplacement du palladium et de l'or, respectivement. Par exemple, la ductilité en compression des alliages Ti50Pd35.5Nb14.5, Ti50Pd32Fe18 et Ti44.5Pd35Nb11Fe9.5 (% at.) n'est pas significativement différente de celle d'un alliage binaire équi-atomique TiPd, tel que visible sur la
Les éléments d'un troisième groupe comportant : Cr, Mn, Cu, Zn et Ag, peuvent être introduits en quantité limitée (<10% at.) dans les alliages TiPd et TiAu en remplacement du palladium et de l'or, respectivement.The elements of a third group comprising: Cr, Mn, Cu, Zn and Ag, can be introduced in a limited quantity (<10% at.) In the TiPd and TiAu alloys to replace palladium and gold, respectively.
Finalement, les éléments d'un quatrième groupe comportant : Al, Si, Ge, Sn, Sb et In, peuvent être introduits en faible quantité (<4% at.) dans les alliages TiPd et TiAu en remplacement du titane ou du palladium et de l'or, respectivement.Finally, the elements of a fourth group comprising: Al, Si, Ge, Sn, Sb and In, can be introduced in small quantities (<4% at.) In the TiPd and TiAu alloys, replacing titanium or palladium and gold, respectively.
Idéalement, pour des applications en contact avec le corps humain, les matériaux de substitution ne doivent pas générer de risques pour la santé. Pour réduire efficacement le surcoût dû à la présence de métal précieux, les matériaux de substitution de ce dernier ne doivent pas être précieux. Finalement, afin de ne pas trop alourdir l'alliage, les matériaux de substitution, idéalement, ne sont pas plus lourds que le métal substitué.Ideally, for applications in contact with the human body, the substitute materials should not pose a health risk. To effectively reduce the additional cost due to the presence of precious metal, substitute materials for the latter should not be valuable. Finally, in order not to not too heavy the alloy, the substitute materials, ideally, are not heavier than the substituted metal.
Une mise en œuvre particulièrement avantageuse de l'invention concerne la substitution d'une partie du palladium dans un alliage TiPd.A particularly advantageous implementation of the invention relates to the substitution of a part of the palladium in a TiPd alloy.
L'invention concerne alors un alliage ductile basé sur l'intermétallique équi-atomique Ti-Pd, dans lequel le surplus de palladium par rapport au titre massique de Pd500 est partiellement ou totalement remplacé par un élément non précieux, de telle sorte que le titane représente toujours 50% atomique de l'alliage final. Un tel alliage présente une ductilité suffisante pour offrir une formabilité similaire à celle d'alliages de titane conventionnels.The invention therefore relates to a ductile alloy based on the equi-atomic intermetallic Ti-Pd, in which the excess of palladium relative to the mass content of Pd500 is partially or totally replaced by a non-precious element, such that the titanium always represents 50 atomic% of the final alloy. Such an alloy has sufficient ductility to provide formability similar to that of conventional titanium alloys.
Il s'agit donc de réduire le surtitrage, par une substitution d'une partie du palladium, sans impacter défavorablement la ductilité.It is therefore a question of reducing the over-titration, by substituting a part of the palladium, without adversely impacting the ductility.
Les alliages ternaires TiPdFe et TiPdNb permettent d'atteindre le titre souhaité. Tout particulièrement, les alliages TiPdNb ne présentent pas d'effet parasite de mémoire de forme, ce qui est avantageux.The ternary TiPdFe and TiPdNb alloys make it possible to achieve the desired titer. In particular, the TiPdNb alloys do not exhibit any parasitic shape memory effect, which is advantageous.
La composition de l'alliage peut être formulée selon une des compositions suivantes, où toutes les fractions sont atomiques :The composition of the alloy can be formulated according to one of the following compositions, where all the fractions are atomic:
On remplace une partie du titane par une même quantité atomique de zirconium ou de hafnium, ces trois éléments ayant des propriétés chimiques très proches et étant facilement substituables les uns par les autres :
Tia-x(Zr,Hf)xMyPd1-a-y
- 0.3<a<0.6 ; 0<x<0.15 ; 0.01<y<0.4
- M = un ou plusieurs parmi un premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.
- a définit le décalage par rapport à la composition équi-atomique.
- x définit le degré de remplacement du titane par Zr et Hf.
- y définit la fraction d'élément de substitution.
Ti ax (Zr, Hf) x M y Pd 1-ay
- 0.3 <a <0.6; 0 <x <0.15; 0.01 <y <0.4
- M = one or more from a first group composed of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.
- a defines the offset from the equi-atomic composition.
- x defines the degree of replacement of titanium by Zr and Hf.
- y defines the substitution element fraction.
Tia-x(Zr,Hf)xMyPd1-a-y
0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4
Restriction du taux de Zr, Hf, par rapport à la première composition
Ti ax (Zr, Hf) x M y Pd 1-ay
0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4
Restriction of the rate of Zr, Hf, compared to the first composition
Tia-x(Zr,Hf)xMyPdz
0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4 ; 0.2<z<0.55
Ti ax (Zr, Hf) x M y Pd z
0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4; 0.2 <z <0.55
Tia-x(Zr,Hf)xMyPdz
0.44<a<0.55 ; 0<x<0.05 ; 0.07<y<0.28 ; 0.25<z<0.45
Parmi la quatrième composition, les compositions particulières qui suivent conviennent particulièrement bien :
Ti ax (Zr, Hf) x M y Pd z
0.44 <a <0.55; 0 <x <0.05; 0.07 <y <0.28; 0.25 <z <0.45
Among the fourth composition, the particular compositions which follow are particularly suitable:
Composition selon la quatrième composition, et pour laquelle M comporte un ou plusieurs éléments pris parmi un cinquième groupe comportant : Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.Composition according to the fourth composition, and for which M comprises one or more elements taken from a fifth group comprising: Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.
En substitution totale du palladium, le chrome et le cuivre rendent l'alliage fragile. Le manganèse, le zinc, l'argent, l'aluminium, le silicium, le germanium, l'indium, l'étain et le molybdène peuvent avoir, dans certaines conditions, un effet similaire. Leur teneur doit donc être limitée, et le fer et le niobium sont préférés pour constituer les éléments de substitution majoritaires.In total substitution of palladium, chromium and copper make the alloy brittle. Manganese, zinc, silver, aluminum, silicon, germanium, indium, tin and molybdenum can have a similar effect under certain conditions. Their content must therefore be limited, and iron and niobium are preferred to constitute the majority substitution elements.
Composition selon la cinquième composition, et pour laquelle M comporte Fe et/ou Nb comme éléments majoritaires.Composition according to the fifth composition, and for which M comprises Fe and / or Nb as majority elements.
Composition selon la sixième composition, et contenant 50% en masse de palladium.Composition according to the sixth composition, and containing 50% by mass of palladium.
Plus particulièrement, la composition atomique Ti49.7Pd32Fe15.3Cr3 présente des caractéristiques intéressantes : effet mémoire faible, quantité de deuxième phase faible, et propriétés mécaniques pas trop élevées.More particularly, the atomic composition Ti49.7Pd32Fe15.3Cr3 exhibits interesting characteristics: low memory effect, low amount of second phase, and not too high mechanical properties.
Les compositions de cette neuvième composition contenant atomiquement 12.5 et 10.5 % de niobium présentent un effet mémoire de forme alors que la composition Ti50Pd35.5Nb14.5 de la
De façon générale, de faibles écarts de compositions, notamment concernant celle du titane, de l'ordre de 0,3% du total, ne changent pas foncièrement les propriétés de ces différentes compositions, et n'altèrent pas leur aptitude au remplacement des alliages classiques.In general, small differences in compositions, in particular concerning that of titanium, of the order of 0.3% of the total, do not fundamentally change the properties of these different compositions, and do not alter their suitability for replacing the alloys. classic.
L'invention concerne ainsi un composant d'habillage pour pièce d'horlogerie ou de bijouterie, réalisé en alliage précieux léger comportant du titane et du niobium.The invention thus relates to a trim component for a timepiece or jewelry piece, made of a light precious alloy comprising titanium and niobium.
Selon la première composition voisine de l'invention exposée plus haut, la composition de cet alliage obéit à la composition atomique :
Tia-x(Zr,Hf)xMyPd1-a-y,
avec 0.3<a<0.6, 0<x<0.15, 0.01<y<0.4,
et M étant un ou plusieurs parmi un premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.According to the first composition similar to the invention described above, the composition of this alloy obeys the atomic composition:
Ti ax (Zr, Hf) x M y Pd 1-ay ,
with 0.3 <a <0.6, 0 <x <0.15, 0.01 <y <0.4,
and M being one or more from a first group composed of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al , Si, Ge, Sn, Sb, In.
Plus particulièrement, cet alliage voisin de l'invention comporte entre 15 et 60 % atomique de titane, entre 0 et 69% atomique de palladium, entre 1 et 40% atomique d'or, et le complément à 100% atomique comporte un total compris entre 0 et 15% atomique de zirconium et hafnium, et un ou plusieurs composants pris parmi un sous-groupe du premier groupe composé de : Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.More particularly, this similar alloy of the invention comprises between 15 and 60 atomic% of titanium, between 0 and 69 atomic% of palladium, between 1 and 40 atomic% of gold, and the complement to 100% atomic comprises a total of between 0 and 15 atomic% of zirconium and hafnium, and one or more components taken from a subgroup of the first group consisting of: Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Pt, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, Sb, In.
Dans une alternative voisine de l'invention, l'alliage comporte en % atomique davantage de palladium que d'or.In an alternative similar to the invention, the alloy contains in atomic% more palladium than gold.
Plus particulièrement, dans une composition voisine de l'invention, l'alliage comporte entre 30% et 60% atomique de titane, et le reste du dit alliage comporte une majorité de palladium, et, en quantité supérieure à 10% atomique du total de l'alliage, au moins un métal d'un deuxième groupe comportant : Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.More particularly, in a composition similar to the invention, the alloy comprises between 30% and 60 atomic% of titanium, and the remainder of said alloy comprises a majority of palladium, and, in an amount greater than 10 atomic% of the total of the alloy, at least one metal from a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.
Dans une autre alternative voisine de l'invention, l'alliage comporte entre 30% et 60% atomique de titane, et le reste de cet alliage comporte une majorité d'or, et, en quantité supérieure à 10% atomique du total de l'alliage, au moins un métal d'un deuxième groupe comportant : Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.In another alternative close to the invention, the alloy comprises between 30% and 60 atomic% of titanium, and the remainder of this alloy contains a majority of gold, and, in an amount greater than 10 atomic% of the total of l 'alloy, at least one metal from a second group comprising: Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.
Dans une réalisation particulière voisine de l'invention, l'alliage comporte au moins un métal d'un troisième groupe comportant : Cr, Mn, Cu, Zn et Ag, la quantité globale des métaux dudit troisième groupe est inférieure à 10% atomique du total de l'alliage.In a particular embodiment similar to the invention, the alloy comprises at least one metal from a third group comprising: Cr, Mn, Cu, Zn and Ag, the overall quantity of metals from said third group is less than 10 atomic% of the total of the alloy.
Dans une autre réalisation particulière voisine de l'invention, l'alliage comporte au moins un métal d'un quatrième groupe comportant : Al, Si, Ge, Sn, Sb et In, la quantité globale des métaux du quatrième groupe est inférieure à 4% atomique du total de l'alliage.In another particular embodiment similar to the invention, the alloy comprises at least one metal from a fourth group comprising: Al, Si, Ge, Sn, Sb and In, the overall quantity of metals from the fourth group is less than 4 Atomic% of the total alloy.
Selon l'invention, l'alliage comporte entre 49.0 et 51.0% atomique de titane.According to the invention, the alloy contains between 49.0 and 51.0 atomic% of titanium.
Dans une autre réalisation particulière voisine de l'invention, le total en % atomique du titane, du zirconium, et du hafnium, est compris entre 49.0 et 51.0 % atomique.In another particular embodiment similar to the invention, the total in atomic% of titanium, zirconium and hafnium is between 49.0 and 51.0 atomic%.
Selon la deuxième composition voisine de l'invention exposée plus haut, l'alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPd1-a-y, avec 0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4.According to the second neighboring composition of the invention described above, the alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd 1-ay , with 0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4.
Selon la troisième composition voisine de l'invention exposée plus haut, l'alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPdz, avec 0.3<a<0.6 ; 0<x<0.05 ; 0.01<y<0.4 ; 0.2<z<0.55.According to the third neighboring composition of the invention described above, the alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd z , with 0.3 <a <0.6; 0 <x <0.05; 0.01 <y <0.4; 0.2 <z <0.55.
Selon la quatrième composition voisine de l'invention exposée plus haut, l'alliage obéit à la composition atomique Tia-x(Zr,Hf)xMyPdz, avec 0.44<a<0.55 ; 0<x<0.05 ; 0.07<y<0.28 ; 0.25<z<0.45.According to the fourth neighboring composition of the invention described above, the alloy obeys the atomic composition Ti ax (Zr, Hf) x M y Pd z , with 0.44 <a <0.55; 0 <x <0.05; 0.07 <y <0.28; 0.25 <z <0.45.
Plus particulièrement, selon des variantes de cette quatrième composition voisine de l'invention :
- l'alliage obéit à la composition atomique TirPdsFet, avec r compris entre 49.5 et 50.5 % atomique, s compris entre 31.5 et 32.5% atomique, t compris entre 17.5 et 18.5% atomique, avec r+s+t=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.32Fe0.18.
- l'alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.5 et 50.5% atomique, s compris entre 34.9 et 35.9% atomique, u compris entre 14.1 et 15.1% atomique, avec r+s+u=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.354Nb0.146.
- l'alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.2 et 50.2% atomique, s compris entre 37.3 et 40.3% atomique, u compris entre 10.0 et 13.0% atomique, avec r+s+u=100, avec des variantes selon la neuvième composition exposée ci-dessus :
- l'alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.2 et 50.2% atomique, s compris entre 37.3 et 38.3% atomique, u compris entre 12.0 et 13.0% atomique, avec r+s+u=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.378Nb0.125
- l'alliage obéit à la composition atomique TirPdsNbu, avec r compris entre 49.2 et 50.2% atomique, s compris entre 39.3 et 40.3% atomique, u compris entre 10.0 et 11.0% atomique, avec r+s+u=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.398Nb0.105
- l'alliage obéit à la composition atomique TirPdsAuv, avec r compris entre 49.5 et 50.5% atomique, s compris entre 39.9 et 40.9% atomique, v compris entre 8.5 et 9.5% atomique, avec r+s+v=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.404Au0.09.
- l'alliage obéit à la composition atomique TirPdsCow, avec r compris entre 49.5 et 50.5% atomique, s compris entre 31.8 et 32.8% atomique, w compris entre 17.2 et 18.2% atomique, avec r+s+w=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.323Co0.177.
- l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.5 et 50.5% atomique, s compris entre 31.5 et 32.5% atomique, c compris entre 16.5 et 17.5% atomique, d compris entre 0.5 et 1.5% atomique, avec r+s+c+d=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.50Pd0.32Fe0.17Cr0.01
- l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 9.9 et 15.8% atomique, d compris entre 2.5 et 8.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100. Selon des variantes décrites selon la huitième composition exposée ci-dessus
- l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 14.8 et 15.8% atomique, d compris entre 2.5 et 3.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.32Fe0.153Cr0.03. Selon d'autres variantes :
- l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 11.8 et 12.8% atomique, d compris entre 5.5 et 6.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.32Fe0.123Cr0.06
- l'alliage obéit à la composition atomique TirPdsFecCrd, avec r compris entre 49.2 et 50.2% atomique, s compris entre 31.4 et 32.5% atomique, c compris entre 9.9 et 10.9% atomique, d compris entre 7.7 et 8.5% atomique, avec c+d compris entre 17.8 et 18.9% atomique, avec r+s+c+d=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.497Pd0.319Fe0.104Cr0.08
- l'alliage obéit à la composition atomique TirPdsFeeCuf, avec r compris entre 49.5 et 50.5% atomique, s compris entre 31.5 et 32.5% atomique, e compris entre 16.5 et 17.5% atomique, f compris entre 0.5 et 1.5% atomique, avec r+s+e+f=100. Plus particulièrement dans cette composition voisine de l'invention, l'alliage obéit à la composition atomique Ti0.50Pd0.32Fe0.17Cu0.01.
- l'alliage obéit à la composition atomique TirPdsFegZrh, avec r compris entre 48.5 et 49.5% atomique, s compris entre 31.8 et 32.8% atomique, g compris entre 17.2 et 18.2% atomique, h compris entre 0.5 et 1.5% atomique, avec r+s+g+h=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.49Zr0.01Pd0.323Fe0.177.
- l'alliage obéit à la composition atomique TirPdsFejAlk, avec r compris entre 48.5 et 49.5% atomique, s compris entre 31.2 et 32.2% atomique, j compris entre 16.8 et 17.8% atomique, k compris entre 1.5 et 2.5% atomique, avec r+s+j+k=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.49Pd0.317Fe0.173Al0.02.
- l'alliage obéit à la composition atomique TirPdsFemNbn, avec r compris entre 44.0 et 45.0 % atomique, s compris entre 34.5 et 35.5% atomique, m compris entre 9.0 et 10.0% atomique, n compris entre 10.5 et 11.5% atomique, avec r+s+m+n=100. Plus particulièrement, l'alliage obéit à la composition atomique Ti0.445Pd0.35Nb0.11Fe0.095.
- the alloy obeys the atomic composition Ti r Pd s Fe t , with r between 49.5 and 50.5 atomic%, s between 31.5 and 32.5 atomic%, t between 17.5 and 18.5 atomic%, with r + s + t = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.32 Fe 0.18 .
- the alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.5 and 50.5 atomic%, s between 34.9 and 35.9 atomic%, u between 14.1 and 15.1 atomic%, with r + s + u = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.354 Nb 0.146 .
- the alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.2 and 50.2 atomic%, s between 37.3 and 40.3 atomic%, u between 10.0 and 13.0 atomic%, with r + s + u = 100, with variants according to the ninth composition set out above:
- the alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.2 and 50.2 atomic%, s between 37.3 and 38.3 atomic%, u between 12.0 and 13.0 atomic%, with r + s + u = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.378 Nb 0.125
- the alloy obeys the atomic composition Ti r Pd s Nb u , with r between 49.2 and 50.2 atomic%, s between 39.3 and 40.3 atomic%, u between 10.0 and 11.0 atomic%, with r + s + u = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.398 Nb 0.105
- the alloy obeys the atomic composition Ti r Pd s Au v , with r between 49.5 and 50.5 atomic%, s between 39.9 and 40.9 atomic%, v between 8.5 and 9.5 atomic%, with r + s + v = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.404 Au 0.09 .
- the alloy obeys the atomic composition Ti r Pd s Co w , with r between 49.5 and 50.5 atomic%, s between 31.8 and 32.8 atomic%, w between 17.2 and 18.2 atomic%, with r + s + w = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.323 Co 0.177 .
- the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r between 49.5 and 50.5 atomic%, s between 31.5 and 32.5 atomic%, c between 16.5 and 17.5 atomic%, d between 0.5 and 1.5 atomic%, with r + s + c + d = 100. More particularly, the alloy obeys the atomic composition Ti 0.50 Pd 0.32 Fe 0.17 Cr 0.01
- the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r between 49.2 and 50.2 atomic%, s between 31.4 and 32.5 atomic%, c between 9.9 and 15.8 atomic%, d between 2.5 and 8.5% atomic, with c + d between 17.8 and 18.9% atomic, with r + s + c + d = 100. According to variants described according to the eighth composition set out above
- the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r between 49.2 and 50.2 atomic%, s between 31.4 and 32.5 atomic%, c between 14.8 and 15.8 atomic%, d between 2.5 and 3.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.32 Fe 0.153 Cr 0.03 . According to other variants:
- the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r between 49.2 and 50.2 atomic%, s between 31.4 and 32.5 atomic%, c between 11.8 and 12.8 atomic%, d between 5.5 and 6.5 atomic%, with c + d between 17.8 and 18.9 atomic%, with r + s + c + d = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.32 Fe 0.123 Cr 0.06
- the alloy obeys the atomic composition Ti r Pd s Fe c Cr d , with r between 49.2 and 50.2 atomic%, s between 31.4 and 32.5 atomic%, c between 9.9 and 10.9 atomic%, d between 7.7 and 8.5% atomic, with c + d between 17.8 and 18.9% atomic, with r + s + c + d = 100. More particularly, the alloy obeys the atomic composition Ti 0.497 Pd 0.319 Fe 0.104 Cr 0.08
- the alloy obeys the atomic composition Ti r Pd s Fe e Cu f , with r between 49.5 and 50.5 atomic%, s between 31.5 and 32.5 atomic%, e between 16.5 and 17.5 atomic%, f between 0.5 and 1.5 atomic%, with r + s + e + f = 100. More particularly in this composition similar to the invention, the alloy obeys the atomic composition Ti 0.50 Pd 0.32 Fe 0.17 Cu 0.01 .
- the alloy obeys the atomic composition Ti r Pd s Fe g Zr h , with r between 48.5 and 49.5 atomic%, s between 31.8 and 32.8 atomic%, g between 17.2 and 18.2 atomic%, h between 0.5 and 1.5 atomic%, with r + s + g + h = 100. More particularly, the alloy obeys the atomic composition Ti 0.49 Zr 0.01 Pd 0.323 Fe 0.177 .
- the alloy obeys the atomic composition Ti r Pd s Fe j Al k , with r between 48.5 and 49.5 atomic%, s between 31.2 and 32.2 atomic%, j between 16.8 and 17.8 atomic%, k between 1.5 and 2.5% atomic, with r + s + j + k = 100. More particularly, the alloy obeys the atomic composition Ti 0.49 Pd 0.317 Fe 0.173 Al 0.02 .
- the alloy obeys the atomic composition Ti r Pd s Fe m Nb n , with r between 44.0 and 45.0 atomic%, s between 34.5 and 35.5 atomic%, m between 9.0 and 10.0 atomic%, n between 10.5 and 11.5% atomic, with r + s + m + n = 100. More particularly, the alloy obeys the atomic composition Ti 0.445 Pd 0.35 Nb 0.11 Fe 0.095 .
Selon la cinquième composition voisine de l'invention exposée ci-dessus, M comporte un ou plusieurs éléments pris parmi un cinquième groupe comportant : Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.According to the fifth composition similar to the invention set out above, M comprises one or more elements taken from a fifth group comprising: Nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn , In.
Selon la sixième composition exposée ci-dessus, M comporte Fe et/ou Nb comme éléments majoritaires.According to the sixth composition explained above, M comprises Fe and / or Nb as majority elements.
Selon la septième composition exposée ci-dessus, l'alliage comporte 50% en masse de palladium. Cette proportion en masse du total de l'alliage ne vient naturellement pas en contradiction avec les proportions atomiques des éléments d'alliage, il s'agit ici d'une condition supplémentaire, nullement incompatible.According to the seventh composition explained above, the alloy comprises 50% by weight of palladium. This proportion by mass of the total of the alloy does not naturally come into contradiction with the atomic proportions of the alloying elements, this is an additional condition, in no way incompatible.
La deuxième famille d'alliages décrit des compositions, faisant notamment appel à trois groupes de métaux (groupe principal de métaux et deux sous-groupes de métaux) et à cinq groupes de traces (groupe principal de traces et quatre sous-groupes de traces). Ce qui suit concerne cette deuxième famille.The second family of alloys describes compositions, in particular using three groups of metals (main group of metals and two subgroups of metals) and five groups of traces (main group of traces and four subgroups of traces) . What follows concerns this second family.
Un composant voisin de l'invention concerne un composant d'habillage 1 pour pièce d'horlogerie ou de bijouterie, réalisé en alliage précieux léger de cette deuxième famille d'alliages, comportant du titane et du palladium. Cet alliage obéit à la formulation atomique
TiaPdbMcTd,
où a, b, c, d sont des fractions atomiques du total, telles que a+b+c+d= 1,
avec:
- a compris entre 0.44 et 0.55, bornes comprises,
- b compris entre 0.30 et 0.45, bornes comprises,
- c compris entre 0.04 et 0.24, bornes comprises,
- d compris entre 0.001 et 0.03, bornes comprises,
- où l'alliage comporte au plus deux métaux M, pris parmi un groupe principal de métaux composé de : Nb, V, Fe, Co, Au, Pt, la fraction atomique c étant le total des fractions atomiques des métaux M,
- où la fraction atomique d est le total des fractions atomiques de traces de métaux T, chaque trace de métal T étant prise avec une proportion atomique inférieure à 3,0% du total de l'alliage, les traces de métal T étant prises parmi un groupe principal de traces comportant Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, B, Si, Ge, Sn, Sb, In, à l'exception des métaux M incorporés dans l'alliage, lequel alliage comporte au moins 0.05% de bore en fraction atomique,
- le complément atomique à 100% étant constitué de ces au plus deux métaux M,
- et où l'alliage comporte au moins 50% en masse de palladium.
Ti a Pd b M c T d ,
where a, b, c, d are atomic fractions of the total, such that a + b + c + d = 1,
with:
- a between 0.44 and 0.55, limits included,
- b between 0.30 and 0.45, limits included,
- c between 0.04 and 0.24, limits included,
- d between 0.001 and 0.03, limits included,
- where the alloy comprises at most two metals M, taken from a main group of metals composed of: Nb, V, Fe, Co, Au, Pt, the atomic fraction c being the total of the atomic fractions of the metals M,
- where the atomic fraction d is the total of the atomic fractions of trace metals T, each trace of metal T being taken with an atomic proportion less than 3.0% of the total of the alloy, the traces of metal T being taken from a main group of traces comprising Nb, V, Mo, Ta, W, Fe, Co, Ni, Ru, Rh, Ir, Au, Pt, Cr, Mn, Cu, Zn, Ag, Al, B, Si, Ge, Sn , Sb, In, with the exception of the metals M incorporated in the alloy, which alloy contains at least 0.05% boron in atomic fraction,
- the atomic complement to 100% consisting of these at most two metals M,
- and wherein the alloy comprises at least 50% by weight of palladium.
Plus particulièrement, cet alliage comporte, en proportions atomiques du total, moins de 0.3% de bore.More particularly, this alloy comprises, in atomic proportions of the total, less than 0.3% boron.
Dans une composition particulière à fourchette réduite en titane, ces fractions atomiques a, b, c, d sont telles que :
- a compris entre 0.48 et 0.52, bornes comprises,
- b compris entre 0.30 et 0.43, bornes comprises,
- c compris entre 0.05 et 0.21, bornes comprises,
- d compris entre 0.001 et 0.03, bornes comprises.
- a between 0.48 and 0.52, limits included,
- b between 0.30 and 0.43, limits included,
- c between 0.05 and 0.21, limits included,
- d between 0.001 and 0.03, limits included.
Dans une variante voisine de l'invention dont l'or, le platine et le cobalt sont écartés de la liste des métaux M,
- ces au plus deux métaux M sont pris parmi un premier sous-groupe de métaux composé de : Nb, V, Fe, la fraction atomique c étant le total des fractions atomiques des métaux M,
- a compris entre 0.49 et 0.51, bornes comprises,
- b compris entre 0.30 et 0.38, bornes comprises,
- c compris entre 0.09 et 0.20, bornes comprises,
- d compris entre 0.001 et 0.03, bornes comprises.
- these at most two metals M are taken from a first subgroup of metals composed of: Nb, V, Fe, the atomic fraction c being the total of the atomic fractions of the metals M,
- a between 0.49 and 0.51, limits included,
- b between 0.30 and 0.38, limits included,
- c between 0.09 and 0.20, limits included,
- d between 0.001 and 0.03, limits included.
Plus particulièrement encore dans cette même variante sans or, platine ni cobalt, les traces de métal T sont prises parmi un premier sous-groupe de traces comportant Nb, V, Mo, Ta, W, Fe, Ni, Ru, Rh, Ir, Cr, Mn, Cu, Zn, Ag, Al, B, Si, Ge, Sn, Sb, In, à l'exception des métaux M incorporés dans l'alliage.More particularly still in this same variant without gold, platinum or cobalt, the traces of metal T are taken from a first subgroup of traces comprising Nb, V, Mo, Ta, W, Fe, Ni, Ru, Rh, Ir, Cr, Mn, Cu, Zn, Ag, Al, B, Si, Ge, Sn, Sb, In, with the exception of the metals M incorporated in the alloy.
Plus particulièrement, toujours dans cette même variante sans or, platine ni cobalt, les traces de métal T sont prises parmi un deuxième sous-groupe de traces comportant Nb, V, Fe, Ru, Rh, Au, Pt, Cr, B, à l'exception des métaux M incorporés dans l'alliage.More particularly, still in this same variant without gold, platinum or cobalt, the traces of metal T are taken from a second subgroup of traces comprising Nb, V, Fe, Ru, Rh, Au, Pt, Cr, B, to except for M metals incorporated in the alloy.
Dans une composition voisine de l'invention sans or, platine ni cobalt, et sans vanadium,
- ces au plus deux métaux M, sont pris parmi un deuxième sous-groupe de métaux composé de: Nb, Fe, la fraction atomique c étant le total des fractions atomiques des métaux M,
- a compris entre 0.49 et 0.51, bornes comprises,
- b compris entre 0.30 et 0.38, bornes comprises,
- c compris entre 0.09 et 0.19, bornes comprises,
- d compris entre 0.001 et 0.03, bornes comprises.
- these at most two metals M, are taken from a second subgroup of metals composed of: Nb, Fe, the atomic fraction c being the total of the atomic fractions of the metals M,
- a between 0.49 and 0.51, limits included,
- b between 0.30 and 0.38, limits included,
- c between 0.09 and 0.19, limits included,
- d between 0.001 and 0.03, limits included.
Dans une sous-variante voisine de l'invention où l'alliage comporte un seul métal M constitué par le fer,
- l'alliage obéit à la formulation atomique TiaPdbFecTd,
- les traces de métal T sont prises parmi un troisième sous-groupe de traces comportant Nb, V, Ru, Rh, Au, Pt, Cr, B,
- a compris entre 0.49 et 0.51, bornes comprises,
- b compris entre 0.31 et 0.35, bornes comprises,
- c compris entre 0.11 et 0.19, bornes comprises,
- d compris entre 0.001 et 0.03, bornes comprises.
- the alloy obeys the atomic formulation Ti a Pd b Fe c T d ,
- the traces of metal T are taken from a third subgroup of traces comprising Nb, V, Ru, Rh, Au, Pt, Cr, B,
- a between 0.49 and 0.51, limits included,
- b between 0.31 and 0.35, limits included,
- c between 0.11 and 0.19, limits included,
- d between 0.001 and 0.03, limits included.
Plus particulièrement, dans cette variante où l'alliage comporte un seul métal M constitué par le fer, l'alliage comporte au plus deux traces de métal T prises parmi le chrome et le bore, et les fractions atomiques a, b, c, d sont telles que:
- a compris entre 0.49 et 0.51, bornes comprises,
- b compris entre 0.31 et 0.33, bornes comprises,
- c compris entre 0.14 et 0.19, bornes comprises,
- d compris entre 0.010 et 0.030, bornes comprises.
- a between 0.49 and 0.51, limits included,
- b between 0.31 and 0.33, limits included,
- c between 0.14 and 0.19, limits included,
- d between 0.010 and 0.030, limits included.
Un autre alliage voisin de l'invention comporte une seule trace de métal T constituée par le chrome, l'alliage obéissant à la formulation atomique TiaPdbFecCrd.Another similar alloy of the invention comprises a single trace of metal T constituted by chromium, the alloy obeying the atomic formulation Ti a Pd b Fe c Cr d .
L'alliage selon l'invention comporte un seul métal M constitué par le niobium, l'alliage obéit à la formulation atomique TiaPdbNbcTd,
- les traces de métal T sont prises parmi un quatrième sous-groupe de traces comportant V, Ru, Rh, Au, Pt, Cr, B,
- et les fractions atomiques a, b, c, d sont telles que:
- a compris entre 0.49 et 0.51, bornes comprises,
- b compris entre 0.34 et 0.38, bornes comprises,
- c compris entre 0.09 et 0.16, bornes comprises,
- d compris entre 0.001 et 0.03, bornes comprises.
- the traces of metal T are taken from a fourth subgroup of traces comprising V, Ru, Rh, Au, Pt, Cr, B,
- and the atomic fractions a, b, c, d are such that:
- a between 0.49 and 0.51, limits included,
- b between 0.34 and 0.38, limits included,
- c between 0.09 and 0.16, limits included,
- d between 0.001 and 0.03, limits included.
Dans une composition particulière de cette sous-variante où l'alliage comporte un seul métal M constitué par le niobium, l'alliage comporte au plus deux traces de métal T prises parmi le chrome et le bore, et les fractions atomiques a, b, c, d sont telles que:
- a compris entre 0.49 et 0.51, bornes comprises,
- b compris entre 0.34 et 0.36, bornes comprises,
- c compris entre 0.11 et 0.15, bornes comprises,
- d compris entre 0.010 et 0.030, bornes comprises.
- a between 0.49 and 0.51, limits included,
- b between 0.34 and 0.36, limits included,
- c between 0.11 and 0.15, limits included,
- d between 0.010 and 0.030, limits included.
Dans une autre composition de cette même sous-variante où l'alliage comporte un seul métal M constitué par le niobium, l'alliage comporte une seule trace de métal T constituée par le chrome, l'alliage obéit à la formulation atomique
TiaPdbNbcCrd,
et les fractions atomiques a, b, c, d sont telles que:
- a compris entre 0.49 et 0.51, bornes comprises,
- b compris entre 0.34 et 0.36, bornes comprises,
- c compris entre 0.11 et 0.15, bornes comprises,
- d compris entre 0.010 et 0.030, bornes comprises.
Ti a Pd b Nb c Cr d ,
and the atomic fractions a, b, c, d are such that:
- a between 0.49 and 0.51, limits included,
- b between 0.34 and 0.36, limits included,
- c between 0.11 and 0.15, limits included,
- d between 0.010 and 0.030, limits included.
Pour l'ensemble de cette deuxième famille d'alliages, on peut avantageusement réduire le taux de palladium pour réduire le coût de l'alliage.For all of this second family of alloys, the level of palladium can advantageously be reduced to reduce the cost of the alloy.
Ainsi, selon l'invention, la teneur massique du palladium est inférieure ou égale à 51.0% du total de l'alliage.Thus, according to the invention, the mass content of palladium is less than or equal to 51.0% of the total of the alloy.
L'invention concerne encore une pièce d'horlogerie 10 ou de bijouterie, notamment une montre, comportant au moins un tel élément d'habillage 1.The invention also relates to a
En résumé, pour l'ensemble des compositions selon l'invention, les différents alliages sélectionnés ci-dessus sont ductiles, et permettent donc une mise en forme par les procédés habituels de déformation.In summary, for all of the compositions according to the invention, the various alloys selected above are ductile, and therefore allow shaping by the usual deformation methods.
Ces alliages sont encore :
- précieux, au sens légal du terme (aloi) ;
- particulièrement légers en comparaison avec la majorité des alliages précieux, au sens légal du terme ;
- sans danger pour le corps humain ;
- très résistants à la corrosion.
- precious, in the legal sense of the term (aloi);
- particularly light in comparison with the majority of precious alloys, in the legal sense of the term;
- harmless to the human body;
- very resistant to corrosion.
La réalisation d'éléments d'habillage horloger dans l'alliages cités selon l'invention bénéficie de l'optimisation de la composition de l'alliage selon différents angles :
- ajout d'éléments abaissant le point de fusion afin de faciliter la mise en œuvre ;
- modification de la teneur en élément de remplacement du métal précieux afin de modifier les propriétés mécaniques de l'alliage ;
- diverses modifications légères visant à obtenir des alliages à durcissement structural.
- addition of elements lowering the melting point to facilitate processing;
- modification of the content of the replacement element of the precious metal in order to modify the mechanical properties of the alloy;
- various slight modifications aimed at obtaining age-hardening alloys.
La sélection des alliages avec composants de substitution selon l'invention permet, encore, de supprimer l'effet mémoire de forme observé dans la plupart des alliages de base décrits. Par exemple, l'alliage Ti0.5Pd0.354Nb0.146 présente un effet mémoire de forme quasi nul.The selection of the alloys with substitution components according to the invention also makes it possible to eliminate the shape memory effect observed in most of the base alloys described. For example, the Ti 0.5 Pd 0.354 Nb 0.146 alloy has an almost zero shape memory effect.
L'invention autorise de nombreuses applications, et, notamment et de façon non limitative :
- éléments d'habillage: carrures, fonds, lunettes de montres, et éléments d'habillage externe (poussoirs, fermoirs, bracelets) ;
- bijoux, composants de mouvement et d'habillage interne de montres.
- trim elements: middle parts, backs, watch bezels, and external trim elements (pushers, clasps, bracelets);
- jewelry, movement components and internal watch casings.
Claims (4)
- Watch external component (1), taken from middle part, back, bezel, bracelet, clasp, the material of which is a titratable alloy, characterised in that said alloy includes at least titanium and palladium, the mass content of palladium being at least 50.0%, and less than or equal to 51.0% of the total of said alloy, and in that:- said alloy includes niobium and conforms to the atomic formula iaPdbMcTd, where a, b, c, d are atomic fractions of the total, such that a+b+c+d= 1.- where the atomic fraction d is the sum of the atomic fractions of metal traces T, each said metal trace T being taken with an atomic proportion of less than 3.0% of the total of said alloy, which alloy includes at least 0.05% of boron in atomic fraction, said metal traces T are taken from a sub-group of traces including V, Ru, Rh, Au, Pt, Cr, B,- the atomic complement to 100% consisting of niobium,- and said atomic fractions a, b, c, d are such that:- a is comprised between 0.49 and 0.51 inclusive,- b is comprised between 0.34 and 0.38 inclusive,- c is comprised between 0.09 and 0.16 inclusive,- d is comprised between 0.001 and 0.03 inclusive.
- External component (1) according to claim 1, characterised in that said alloy includes, in atomic proportions of the total, less than 0.3% of boron.
- External component (1) according to claim 1 or 2, characterised in that said alloy includes at most two said metal traces T taken from among chromium and boron, and in that said atomic fractions a, b, c, d are such that:- a is comprised between 0.49 and 0.51 inclusive,- b is comprised between 0.34 and 0.36 inclusive,- c is comprised between 0.11 and 0.15 inclusive,- d is comprised between 0.010 and 0.030 inclusive.
- Timepiece (10) or piece of jewellery including at least one external component (1) according to one claims 1 to 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14200381.3A EP3040790A1 (en) | 2014-12-29 | 2014-12-29 | Timepiece or piece of jewellery made of a light titanium-based precious alloy |
| PCT/EP2015/080211 WO2016107752A1 (en) | 2014-12-29 | 2015-12-17 | Timepiece or jewellery item made from lightweight precious alloy comprising titanium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3241078A1 EP3241078A1 (en) | 2017-11-08 |
| EP3241078B1 true EP3241078B1 (en) | 2021-05-26 |
Family
ID=52130164
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP14200381.3A Withdrawn EP3040790A1 (en) | 2014-12-29 | 2014-12-29 | Timepiece or piece of jewellery made of a light titanium-based precious alloy |
| EP15810677.3A Active EP3241078B1 (en) | 2014-12-29 | 2015-12-17 | Timepiece or jewellery item made from lightweight precious alloy comprising titanium |
| EP15817229.6A Active EP3240915B1 (en) | 2014-12-29 | 2015-12-17 | Lightweight precious alloy made from titanium and gold, and timepiece or jewellery item component made from a lightweight precious alloy of titanium and gold |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP14200381.3A Withdrawn EP3040790A1 (en) | 2014-12-29 | 2014-12-29 | Timepiece or piece of jewellery made of a light titanium-based precious alloy |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15817229.6A Active EP3240915B1 (en) | 2014-12-29 | 2015-12-17 | Lightweight precious alloy made from titanium and gold, and timepiece or jewellery item component made from a lightweight precious alloy of titanium and gold |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US10206465B2 (en) |
| EP (3) | EP3040790A1 (en) |
| JP (2) | JP6389561B2 (en) |
| CN (2) | CN107208187B (en) |
| HK (1) | HK1243743B (en) |
| WO (2) | WO2016107752A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3572549A1 (en) | 2018-05-24 | 2019-11-27 | Richemont International S.A. | Jewellery item |
| CN109881044B (en) * | 2019-04-11 | 2021-07-27 | 福建工程学院 | High-hardness and high-wear-resistance titanium alloy and preparation method and application thereof |
| EP3889691B1 (en) * | 2019-05-07 | 2024-02-21 | Nivarox-FAR S.A. | Horological hairspring made of a nb-hf alloy |
| CN110284021B (en) * | 2019-06-27 | 2020-06-30 | 袁海 | Intermediate alloy for improving hardness of pure gold and pure silver and preparation method and application thereof |
| EP3800511B1 (en) * | 2019-10-02 | 2022-05-18 | Nivarox-FAR S.A. | Pivoting shaft for a regulating organ |
| CN112813299A (en) * | 2019-11-12 | 2021-05-18 | 新疆大学 | High-strength low-cost corrosion-resistant titanium alloy |
| CN111020272A (en) * | 2019-12-14 | 2020-04-17 | 深圳晶辉应用材料有限公司 | High-performance gold-based silver-palladium alloy bonding material |
| EP4026923A1 (en) | 2021-01-07 | 2022-07-13 | Officine Panerai AG | Gold and titanium based alloy |
| CN115178913B (en) * | 2022-09-13 | 2023-01-10 | 中国航发北京航空材料研究院 | Brazing filler metal and preparation method and brazing method thereof |
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2015
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- 2015-12-17 WO PCT/EP2015/080211 patent/WO2016107752A1/en active Application Filing
- 2015-12-17 CN CN201580071445.1A patent/CN107208187B/en active Active
- 2015-12-17 EP EP15810677.3A patent/EP3241078B1/en active Active
- 2015-12-17 CN CN201580028804.5A patent/CN106460094B/en active Active
- 2015-12-17 JP JP2017507083A patent/JP6389561B2/en active Active
- 2015-12-17 EP EP15817229.6A patent/EP3240915B1/en active Active
- 2015-12-17 WO PCT/EP2015/080270 patent/WO2016107755A1/en active Application Filing
- 2015-12-17 US US15/308,185 patent/US10136708B2/en active Active
- 2015-12-17 JP JP2017546041A patent/JP6514354B2/en active Active
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2018
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Also Published As
| Publication number | Publication date |
|---|---|
| US10206465B2 (en) | 2019-02-19 |
| US20170226613A1 (en) | 2017-08-10 |
| WO2016107752A4 (en) | 2016-09-15 |
| EP3240915B1 (en) | 2020-07-08 |
| JP2017518442A (en) | 2017-07-06 |
| EP3040790A1 (en) | 2016-07-06 |
| JP6389561B2 (en) | 2018-09-12 |
| EP3241078A1 (en) | 2017-11-08 |
| US10136708B2 (en) | 2018-11-27 |
| WO2016107752A1 (en) | 2016-07-07 |
| JP2018503480A (en) | 2018-02-08 |
| EP3240915A1 (en) | 2017-11-08 |
| CN106460094B (en) | 2019-05-14 |
| CN106460094A (en) | 2017-02-22 |
| WO2016107755A1 (en) | 2016-07-07 |
| CN107208187A (en) | 2017-09-26 |
| US20170367446A1 (en) | 2017-12-28 |
| JP6514354B2 (en) | 2019-05-15 |
| HK1243743B (en) | 2020-03-20 |
| CN107208187B (en) | 2019-02-19 |
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