HK1243743A1 - 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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Description
Technical Field
The invention relates to an exterior part for a timepiece or jewelry made of a light noble metal alloy containing titanium.
The invention also relates to a timepiece or piece of jewellery including at least one such external component.
The present invention relates to the field of external members for timepieces and jewellery.
Background
A common feature of most precious metal alloys used in horology is their relatively high density: (>10g/cm3). In fact, the two main noble metals used in horology, namely gold and platinum, have about 19.3 and 21.5g/cm respectively3The density of (c). This therefore makes their alloys relatively heavy. Silver and palladium were lighter (10.5 and 12g/cm, respectively)3) But is rarely used in watchmaking.
Furthermore, the use of light metals, such as titanium, and to a lesser extent aluminium, is more common in watch exterior parts. However, few alloys are currently considered to be both precious (i.e., to meet purity requirements) and lightweight.
WO patent application 2012/119647A1 describes that lower densities can be achieved (R) ((R))<8g/cm3) Ceramic/precious metal composites of (a).
Generally, it is not possible to obtain ductile metals by alloying light metals and precious metals, and this results in brittle mesophases in almost all cases.
However, there are exceptions to the equiatomic Ti (Pd/Pt/Au) phase. In fact, these phases may be similar to the equiatomic TiNi phases used in some shape memory alloys. Likewise, the equiatomic TiPd, TiPt, and TiAu phases have some ductility and may exhibit properties common to TiNi shape memory alloys under certain conditions. Equiatomic TiPd, TiPt and TiAu alloys have been known for a long time and are the subject of a number of studies on high temperature shape memory alloys.
The effect of adding alloying elements other than Ni, Pd, Pt, and Au to these systems was mainly studied for the TiNi alloy. Studies on ternary additions of TiPd, TiPt and TiAu alloys are not common. However, the addition of iron to the TiPd system is known to have an effect on the phase transition of the system.
Most documents relating to the addition of binary isoatomic alloys of TiNi, TiPd, TiPt and TiAu focus on the modification of the shape memory properties and the so-called superelastic properties (amplitude, transition temperature) of these alloys. However, the problems of using these alloys in jewelry/watch making and the associated constraints, i.e. formability and purity (percentage of precious metals), have not been studied.
The mass composition of the ductility equiatomic phases of the alloys of TiPd, TiPt and TiAu is shown in Table 1, and Table 1 lists the compositions of the equiatomic Ti- (Pd, Pt, Au) phases and a comparison with the legal purity standards adopted by Switzerland.
It should be noted that the TiPd and TiAu alloys meet the purity requirements and are therefore advantageous for watch and jewelry manufacture as particularly light precious metals.
European patent 0267318 in the name of HAFNER lists certain palladium alloys: 25-50% by mass of palladium comprising 37-69% silver, the remainder being copper, zinc, gallium, cobalt, indium, tin, iron, aluminum, nickel, germanium, rhenium, but not titanium, and other alloys having 51-95% palladium with the addition of different metals, of which only one alloy comprises gold with 70% palladium, 15% silver, 5% copper, 5% zinc, 3% platinum, 2% gold by mass. The only composition disclosed containing titanium is Ti5Pd95Type, it relates to alloys comprising 5% titanium and 95% palladium.
European patent 0239747 in the name of sumitoto describes the addition of 0.001-20% chromium to an alloy of the titanium-palladium type containing from 40 to 60 atomic percent of titanium and the remainder being palladium. Several alloys are disclosed that contain 50 atomic percent titanium, 40 to 50 atomic percent palladium, and 0 to 10 atomic percent chromium: ti50Pd40、Ti50Pd45Cr5、Ti50Pd43Cr7、Ti50Pd42Cr8、Ti50Pd41.5Cr8.5、Ti50Pd41Cr9、Ti50Pd40Cr10。
Switzerland patent 704233 in the name of RICHEMONT describes the use of titanium alloys of the Ti-10-2-3 type containing vanadium, iron and aluminum, of the Ti-13-11-3 type containing vanadium, chromium and aluminum, of the Ti-15-3 type containing vanadium, chromium, aluminum and tin, and of the Ti-5-5-5-3 type containing aluminum, vanadium, molybdenum and chromium, in the manufacture of a timepiece. These alloys do not contain palladium or gold.
Disclosure of Invention
The invention proposes to make watch outer parts that are expensive (to benefit from purity and wear and corrosion resistance) and at the same time lighter than the known alloys.
To this end, the invention relates to an external member for a timepiece or jewelry according to claim 1.
The invention also relates to a timepiece or piece of jewellery including at least one such external component.
Drawings
Other features and advantages of the present invention will become apparent upon reading the following detailed description and upon reference to the drawings in which:
figure 1 compares the stress-deformation curves for alloys tested in compression at a deformation speed of 0.001/s:
οTi50Pd35.5Nb14.5with the use of the dashed lines,
οTi50Pd32Fe18with the solid lines being used,
οTi44.5Pd35Nb11Fe9.5by adopting the dotted line,
οTi50Pd50dot-dash lines are used.
Figure 2 shows a watch according to the invention comprising a case and a bracelet.
Detailed Description
All concentrations stated in the following description are atomic percentages unless otherwise indicated.
The present invention relates to the replacement of gold and palladium in alloys comprising titanium.
The invention relates to an external member 1 for a timepiece or piece of jewellery (including jewels of precious stones) made of a light noble metal alloy containing titanium, and any timepiece or piece of jewellery including such a member.
The invention relates to two alloy families which are described in succession. The first alloy family includes nine exemplary compositions (first through ninth) employing five metal groups (first through seventh) and some subgroups thereof.
The use of alloys such as those listed above in table 1, which contain more noble metals than are required for their purity certification, results in unnecessary additional costs. To solve this problem, an advantageous alternative may be applied to additional noble metals, in particular metals from the second group, including: fe. Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.
These elements can be added in large quantities (> 10 atomic percent) to the TiPd and TiAu alloys as substitutes for palladium and gold, respectively. For example, alloy Ti50Pd35.5Nb14.5、Ti50Pd32Fe18And Ti44.5Pd35Nb11Fe9.5(at.%) compressive ductility did not differ significantly from that of the binary equiatomic TiPd alloy, as shown in FIG. 1 for an alloy Ti that was compression tested at a deformation rate of 0.001/s50Pd35.5Nb14.5、Ti50Pd32Fe18、Ti44.5Pd35Nb11Fe9.5And Ti50Pd50The stress-deformation curves of (a) were compared.
Elements of the third group comprising Cr, Mn, Cu, Zn and Ag may be added to the TiPd and Au alloys in limited amounts (< 10 at.%) as substitutes for palladium and gold, respectively.
Finally, elements of the fourth group comprising Al, Si, Ge, Sn, Sb and In may be added to the TiPd and TiAu alloys In small amounts (<4 at.%) as substitutes for titanium or palladium and gold, respectively.
Ideally, for applications in contact with human skin, the substitute material should not pose a health risk. To effectively reduce the additional cost due to the presence of precious metals, materials to replace precious metals should not be precious. Finally, to avoid making the alloy too heavy, the replacement material should ideally not be heavier than the metal being replaced.
A particularly advantageous embodiment of the invention relates to the replacement of a portion of the palladium in the TiPd alloy.
The invention therefore relates to a ductile alloy based on the equiatomic intermetallic compound Ti-Pd, in which any excess palladium in relation to the mass content required for the purity standard Pd500 is partially or completely replaced by non-noble metal elements, so that titanium still occupies 50 atomic percent of the final alloy. This alloy has sufficient ductility to provide formability similar to conventional titanium alloys.
This is therefore a problem of reducing the excess purity by replacing a portion of the palladium, without adversely affecting the ductility.
The ternary alloys TiPdFe and TiPdNb are capable of achieving the desired purity. More specifically, the TiPdNb alloy does not have an undesirable shape memory effect, which is advantageous.
The composition of the alloy may be tailored according to one of the following compositions, where all fractions are atomic fractions:
the first composition is as follows:
a portion of the titanium is replaced by zirconium or hafnium of the same atomic number, since these three elements have very close chemical properties and can easily be replaced by each other.
Tia-x(Zr,Hf)xMyPd1-a-y
0.3<a<0.6；0<x<0.15；0.01<y<0.4
M ═ one or more elements from a first group consisting 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 differences with respect to the isoatomic composition.
x defines the degree of titanium substitution by Zr and Hf.
y defines the score of the substitute element.
A second composition:
Tia-x(Zr,Hf)xMyPd1-a-y
0.3<a<0.6；0<x<0.05；0.01<y<0.4
the content of Zr, Hf is limited with respect to the first composition.
The third composition is as follows:
Tia-x(Zr,Hf)xMyPdz
0.3<a<0.6；0<x<0.05；0.01<y<0.4；0.2<z<0.55
and the fourth composition is as follows:
Tia-x(Zr,Hf)xMyPdz
0.44<a<0.55；0<x<0.05；0.07<y<0.28；0.25<z<0.45
according to a fourth composition, the following specific compositions are particularly suitable:
| Ti0.5Pd0.32Fe0.18 | a＝0.5，x＝0，y＝0.18，z＝0.32 |
| Ti0.5Pd0.354Nb0.146 | a＝0.5，x＝0，y＝0.146，z＝0.354 |
| Ti0.5Pd0.404Au0.09 | a＝0.5，x＝0，y＝0.096，z＝0.404 |
| Ti0.5Pd0.323Co0.177 | a＝0.5，x＝0，y＝0.177，z＝0.323 |
| Ti0.5Pd0.32Fe0.17Cr0.01 | a＝0.5，x＝0，y＝0.18，z＝0.32 |
| Ti0.5Pd0.32Fe0.17Cu0.01 | a＝0.5，x＝0，y＝0.18，z＝0.32 |
| Ti0.49Zr0.01Pd0.323Fe0.177 | a＝0.5，x＝0.01，y＝0.177，z＝0.323 |
| Ti0.49Pd0.317Fe0.173Al0.02 | a＝0.49，x＝0，y＝0.193，z＝0.317 |
| Ti0.445Pd0.35Nb0.11Fe0.095 | a＝0.445，x＝0，y＝0.205，z＝0.35 |
the fifth component:
a composition according to the fourth composition, wherein M comprises one or more elements selected from a fifth group comprising: nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.
As a total replacement for palladium, chromium and copper make the alloy brittle. Manganese, zinc, silver, aluminum, silicon, germanium, indium, tin, and molybdenum may have similar effects under certain conditions. Their content must be limited, and iron and niobium are preferred as the main substitute elements.
The sixth composition is as follows:
a composition according to the fifth composition, wherein M includes Fe and/or Nb as a main element.
The seventh composition is as follows:
a composition according to the sixth composition, and contains 50% by mass of palladium.
The eighth component:
TiPdFeCr alloy
More specifically, the atomic composition Ti49.7Pd32Fe15.3Cr3Has the following advantageous properties: low memory effect, low number of second phases, and not too high mechanical properties.
Ninth composition:
TiPdNb alloy
The ninth composition of the composition comprising 12.5 and 10.5 at.% niobium had a shape memory effect, while the Ti of fig. 1 comprising 14.5% niobium50Pd35.5Nb14.5The composition does not have this effect. This composition comprising 14.5% niobium departs from these effects due to its biphasic nature.
Generally, small compositional differences, particularly with respect to titanium, amounting to about 0.3% do not radically alter the properties of these different compositions and do not impair their suitability for replacing conventional alloys.
The invention therefore relates to an external component for a timepiece or jewelry made of a light noble metal alloy comprising titanium. According to the first composition set forth above, the composition of this alloy corresponds to the atomic composition:
Tia-x(Zr,Hf)xMyPd1-a-y，
wherein 0.3< a <0.6, 0< x <0.15, 0.01< y <0.4,
and, M is one or more elements from a first group consisting 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.
More particularly, this alloy comprises 15-60 at.% titanium, 0-69 at.% palladium, 1-40 at.% gold, and the remainder of 100 at.% comprises 0-15 at.% in total of zirconium and hafnium, and one or more constituents 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.
In one alternative, the alloy contains a higher atomic percentage of palladium than gold.
More particularly, the alloy comprises 30 at.% to 60 at.% titanium, and the remaining constituents of said alloy comprise palladium as a majority and at least one metal from a second group comprising the following elements in an amount greater than 10 at.% of the total alloy: fe. Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.
In another alternative, the alloy comprises 30 at.% to 60 at.% titanium, and the remainder of the alloy comprises gold as a majority and at least one metal from a second group comprising the following elements in an amount greater than 10 at.% of the total alloy: fe. Co, Ni, Ru, Rh, Ir, Au, Pt, Nb, V, Mo, Ta, W.
In a particular embodiment, the alloy comprises at least one metal from a third group comprising the following elements: cr, Mn, Cu, Zn, and Ag, the total amount of the metals of the third group being less than 10 atomic percent of the total alloy.
In another particular embodiment, the alloy comprises at least one metal from a fourth group comprising the following elements: al, Si, Ge, Sn, Sb and In, the total amount of the metals of the fourth group being less than 4 atomic percent of the total alloy.
In a particular embodiment, the alloy includes 49.0-51.0 at.% titanium.
In another particular embodiment, the total atomic percent of titanium, zirconium, and hafnium is between 49.0-51.0 at.%.
In the second composition set forth above, the alloy conforms to the atomic composition Tia-x(Zr，Hf)xMyPd1-a-yWherein 0.3<a<0.6；0<x<0.05；0.01<y<0.4。
In the third composition set forth above, the alloy conforms to the atomic composition Tia-x(Zr,Hf)xMyPdzWherein 0.3<a<0.6；0<x<0.05；0.01<y<0.4；0.2＜z＜0.55。
In the fourth composition set forth above, the alloy conforms to the atomic composition Tia-x(Zr,Hf)xMyPdzWherein 0.44<a<0.55；0<x<0.05；0.07<y<0.28；0.25<z<0.45。
More particularly, according to a variant of this fourth composition:
the alloy corresponding to the atomic composition TirPdsFetWherein r is between 49.5-50.5 at.%, s is between 31.5-32.5 at.%, and t is between 17.5-18.5 at.%, wherein r + s + t is 100. More particularly, the alloy conforms to the atomic composition Ti0.50Pd0.32Fe0.18。
The alloy corresponding to the atomic composition TirPdsNbuWherein r is between 49.5-50.5 at.%, s is between 34.9-35.9 at.%, and u is between 14.1-15.1 at.%, wherein r + s + u is 100. More particularly, the alloy conforms to the atomic composition Ti0.50Pd0.354Nb0.146。
The alloy corresponding to the atomic composition TirPdsNbuWherein r is between 49.2-50.2 at.%, s is between 37.3-40.3 at.%, and u is between 10.0-13.0 at.%, wherein r + s + u is 100. Also, according to the variation of the ninth composition set forth above:
the alloy corresponding to the atomic composition TirPdsNbuWherein r is between 49.2-50.2 at.%, s is between 37.3-38.3 at.%, and u is between 12.0-13.0 at.%, wherein r + s + u is 100. More particularly, the alloy conforms to the atomic composition Ti0.497Pd0.378Nb0.125。
The alloy corresponding to the atomic composition TirPdsNbuWherein r is between 49.2-50.2 at.%, s is between 39.3-40.3 at.%, and u is between 10.0-11.0 at.%, wherein r + s + u is 100. More particularly, the alloy conforms to the atomic composition Ti0.497Pd0.398Nb0.105。
The alloy corresponding to the atomic composition TirPdsAuvWhereinr is between 49.5-50.5 at.%, s is between 39.9-40.9 at.%, v is between 8.5-9.5 at.%, wherein r + s + v is 100. More particularly, the alloy conforms to the atomic composition Ti0.50Pd0.404Au0.09。
The alloy corresponding to the atomic composition TirPdsCowWherein r is between 49.5-50.5 at.%, s is between 31.8-32.8 at.%, and w is between 17.2-18.2 at.%, wherein r + s + w is 100. More particularly, the alloy conforms to the atomic composition Ti0.50Pd0.323Co0.177。
The alloy corresponding to the atomic composition TirPdsFecCrdWherein r is between 49.5-50.5 at.%, s is between 31.5-32.5 at.%, c is between 16.5-17.5 at.%, d is between 0.5-1.5 at.%, wherein r + s + c + d is 100. More particularly, the alloy conforms to the atomic composition Ti0.50Pd0.32Fe0.17Cr0.01。
The alloy corresponding to the atomic composition TirPdsFecCrdWherein r is between 49.2-50.2 at.%, s is between 31.4-32.5 at.%, c is between 9.9-15.8 at.%, d is between 2.5-8.5 at.%, c + d is between 17.8-18.9 at.%, wherein r + s + c + d is 100. According to a variation described based on the eighth composition set forth above:
the alloy corresponding to the atomic composition TirPdsFecCrdWherein r is between 49.2-50.2 at.%, s is between 31.4-32.5 at.%, c is between 14.8-15.8 at.%, d is between 2.5-3.5 at.%, c + d is between 17.8-18.9 at.%, wherein r + s + c + d is 100. More particularly, the alloy conforms to the atomic composition Ti0.497Pd0.32Fe0.153Cr0.03. According to other variants:
the alloy corresponding to the atomic composition TirPdsFecCrdWherein r is between 49.2-50.2 at.%, s is between 31.4-32.5 at.%, c is between 11.8-12.8 at.%D is between 5.5-6.5 at.%, c + d is between 17.8-18.9 at.%, wherein r + s + c + d is 100. More particularly, the alloy conforms to the atomic composition Ti0.497Pd0.32Fe0.123Cr0.06。
The alloy corresponding to the atomic composition TirPdsFecCrdWherein r is between 49.2-50.2 at.%, s is between 31.4-32.5 at.%, c is between 9.9-10.9 at.%, d is between 7.7-8.5 at.%, c + d is between 17.8-18.9 at.%, wherein r + s + c + d is 100. More particularly, the alloy conforms to the atomic composition Ti0.497Pd0.319Fe0.104Cr0.08。
The alloy corresponding to the atomic composition TirPdsFeeCufWherein r is between 49.5-50.5 at.%, s is between 31.5-32.5 at.%, e is between 16.5-17.5 at.%, f is between 0.5-1.5 at.%, wherein r + s + e + f is 100. More particularly, the alloy conforms to the atomic composition Ti0.50Pd0.32Fe0.17Cu0.01。
The alloy corresponding to the atomic composition TirPdsFegZrhWherein r is between 48.5-49.5 at.%, s is between 31.8-32.8 at.%, g is between 17.2-18.2 at.%, h is between 0.5-1.5 at.%, wherein r + s + g + h is 100. More particularly, the alloy conforms to the atomic composition Ti0.49Zr0.01Pd0.323Fe0.177。
The alloy corresponding to the atomic composition TirPdsFejAlkWherein r is between 48.5-49.5 at.%, s is between 31.2-32.2 at.%, j is between 16.8-17.8 at.%, k is between 1.5-2.5 at.%, wherein r + s + j + k is 100. More particularly, the alloy conforms to the atomic composition Ti0.49Pd0.317Fe0.173Al0.02。
The alloy corresponding to the atomic composition TirPdsFemNbnWherein r is between 44.0-45.0 at.%,s is between 34.5-35.5 at.%, m is between 9.0-10.0 at.%, and n is between 10.5-11.5 at.%, wherein r + s + m + n is 100. More particularly, the alloy conforms to the atomic composition Ti0.445Pd0.35Nb0.11Fe0.095。
According to a fifth composition set forth above, M comprises one or more elements selected from a fifth group comprising: nb, Mo, Fe, Cr, Mn, Cu, Zn, Ag, Al, Si, Ge, Sn, In.
According to the sixth composition set forth above, M includes Fe and/or Nb as a main element.
According to the seventh composition set forth above, the alloy contains 50% by mass of palladium. This mass percentage of the alloy must of course not be inconsistent with the atomic proportions of the alloying elements, an additional condition which is in no way incompatible.
The second group of alloys comprises compositions, in particular, composed of three metal groups (one main group of metals and two subgroups of metals) and five trace element groups (one main group of trace elements and four subgroups of trace elements). The following relates to this second group.
The invention relates to an external component 1 for a timepiece or piece of jewellery made of a light noble metal alloy from this second family of alloys comprising titanium and palladium. The alloy conforms to the atomic formula TiaPdbMcTd，
Wherein a, b, c, d are atomic fractions of the total number such that a + b + c + d is 1,
wherein:
a is between 0.44 and 0.55 inclusive,
b is between 0.30 and 0.45 inclusive,
c is between 0.04 and 0.24 inclusive,
d is between 0.001 and 0.03 inclusive,
-wherein the alloy comprises at most two metals M selected from the main group of metals consisting of: nb, V, Fe, Co, Au, Pt, the atomic fraction c being the sum of the atomic fractions of the metal M,
-wherein the atomic fraction d is the sum of the atomic fractions of the metallic microelements T, each of which is chosen In an atomic proportion of less than 3.0% of the total alloy, the metallic microelements T being chosen from a main group of microelements consisting of 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 metal M incorporated In the alloy, which alloy contains at least 0.05% of boron,
the atoms making up to 100% comprise at most two of these metals M,
-and wherein the alloy comprises at least 50% by mass of palladium.
More particularly, the alloy contains less than 0.3 atomic percent boron.
In a particular composition with reduced titanium content, the atomic fractions a, b, c, d are such that:
a is between 0.48 and 0.52 inclusive,
b is between 0.30 and 0.43 inclusive,
c is between 0.05 and 0.21 inclusive,
d is between 0.001 and 0.03 inclusive.
In a variation where gold, platinum and cobalt are removed from the list of metals M:
-said at most two metals M are selected from a first subgroup of metals consisting of the following elements: nb, V, Fe, the atomic fraction c being the sum of the atomic fractions of the metals M,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51 inclusive,
b is between 0.30 and 0.38 inclusive,
c is between 0.09 and 0.20 inclusive,
d is between 0.001 and 0.03 inclusive.
More particularly, In the same variant without gold, platinum and cobalt, the metallic trace element T is selected from a first subgroup of trace elements 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 metal M incorporated In the alloy.
More particularly, also in the same variant without gold, platinum or cobalt, the metallic trace element T is selected from a second subgroup of trace elements comprising Nb, V, Fe, Ru, Rh, Au, Pt, Cr, B, with the exception of the metal M incorporated in the alloy.
In the same variant without gold, platinum or cobalt and without vanadium,
these up to two metals M are chosen from a second subgroup of metals consisting of the following elements: nb, Fe, the atomic fraction c being the sum of the atomic fractions of the metals M,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51 inclusive,
b is between 0.30 and 0.38 inclusive,
c is between 0.09 and 0.19 inclusive,
d is between 0.001 and 0.03 inclusive.
In a sub-variation wherein the alloy comprises a single metal M consisting of iron,
said alloy conforming to the atomic formula TiaPdbFecTd，
-the metallic trace element T is selected from a third subgroup of trace elements comprising Nb, V, Ru, Rh, Au, Pt, Cr, B,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51 inclusive,
b is between 0.31 and 0.35 inclusive,
c is between 0.11 and 0.19 inclusive,
d is between 0.001 and 0.03 inclusive.
More particularly, in this variant in which the alloy comprises a single metal M consisting of iron, the alloy comprises at most two metallic trace elements T selected from chromium and boron, and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51 inclusive,
b is between 0.31 and 0.33 inclusive,
c is between 0.14 and 0.19 inclusive,
d is between 0.010 and 0.030 inclusive.
More particularly, the alloy comprises a single metallic trace element T consisting of chromium, the alloy conforming to the atomic formula TiaPdbFecCrd。
In another sub-variant in which the alloy comprises a single metal M consisting of niobium,
said alloy conforming to the atomic formula TiaPdbNbcTd，
-the metallic trace element T is selected from a fourth subgroup of trace elements comprising V, Fe, Ru, Rh, Au, Pt, Cr, B,
-and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51 inclusive,
b is between 0.34 and 0.38 inclusive,
c is between 0.09 and 0.16 inclusive,
d is between 0.001 and 0.03 inclusive.
In one particular composition of this sub-variant, in which the alloy comprises a single metal M consisting of niobium, the alloy comprises at most two metallic trace elements T selected from chromium and boron, and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51 inclusive,
b is between 0.34 and 0.36 inclusive,
c is between 0.11 and 0.15 inclusive,
d is between 0.010 and 0.030 inclusive.
In another composition in which the alloy comprises the same sub-variant of a single metal M consisting of niobium, the alloy comprises a single metallic trace element T consisting of chromium, the alloy conforming to the atomic formula TiaPdbNbcCrd，
And the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51 inclusive,
b is between 0.34 and 0.36 inclusive,
c is between 0.11 and 0.15 inclusive,
d is between 0.010 and 0.030 inclusive.
For this whole second group of alloys, the palladium content can advantageously be reduced in order to reduce the cost of the alloy.
Thus, in one variation, the mass content of palladium is less than or equal to 60.0% of the total alloy.
More particularly, the palladium content by mass is less than or equal to 55.0% of the total alloy.
More particularly, the palladium content by mass is less than or equal to 52.5% of the total alloy.
More particularly, the palladium content by mass is less than or equal to 51.0% of the total alloy.
The invention also relates to a timepiece 10 or piece of jewellery, in particular a wristwatch, comprising at least one such external member 1.
In short, the various alloys selected above are ductile for all the compositions according to the invention, thus allowing shaping using the usual deformation processes.
In addition, these alloys:
is precious, in the sense of the law of the term (purity);
particularly light compared to most noble metal alloys, in the sense of law of the term;
no risk to the human body,
very corrosion resistant.
The manufacture of timepiece exterior parts made of one of the above alloys benefits from the optimization of the alloy composition in different ways:
-by adding melting point lowering elements to facilitate implementation;
-modifying the content of the noble metal substitute element to modify the mechanical properties of the alloy;
by making various slight modifications to obtain a structurally hardened alloy.
The choice of alloys according to the invention with alternative compositions also avoids the shape memory effect observed in the majority of the basic alloys. For example, alloy Ti0.5Pd0.354Nb0.146Substantially without shape memory effect.
The invention may have numerous applications, particularly but not exclusively:
-elements external to the movement: middle part of the watch case, back cover of the watch case, bezel and external parts (button, watch buckle, watch chain);
jewellery, components for watch interiors and components for movements.
The claims (modification according to treaty clause 19)
1. An exterior part (1) for a timepiece or jewelry, made of a light noble metal alloy comprising titanium and palladium, characterized in that said alloy conforms to the atomic formula TiaPdbMcTd，
Wherein a, b, c, d are the aggregate atomic fractions such that a + b + c + d =1,
wherein:
a is between 0.44 and 0.55 inclusive,
b is between 0.30 and 0.45 inclusive,
c is between 0.04 and 0.24 inclusive,
-d is between 0.001 and 0.03 inclusive,
-wherein the alloy comprises at most two metals M selected from the main group of metals consisting of: nb, V, Fe, Co, Au, Pt, the atomic fraction c being the sum of the atomic fractions of the metals M,
-wherein the atomic fraction d is the sum of the atomic fractions of metallic microelements T, each of said metallic microelements T being chosen In an atomic proportion of less than 3.0% of the total alloy, said metallic microelements T being chosen from a main group of microelements consisting of 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 said metal M incorporated In said alloy, said alloy containing boron In an atomic fraction of at least 0.05%,
-100% of the remaining atoms consist of the at most two metals M,
-and the alloy comprises at least 50% by mass of palladium, the mass content of palladium being less than or equal to 60.0% of the total alloy.
2. The outer member (1) according to claim 1, wherein the alloy contains less than 0.3 atomic% boron.
3. The outer member (1) according to claim 1, wherein the atomic fractions a, b, c, d are such that:
a is between 0.48 and 0.52 inclusive,
b is between 0.30 and 0.43 inclusive,
c is between 0.05 and 0.21 inclusive,
-d is between 0.001 and 0.03 inclusive.
4. The outer member (1) according to claim 3, wherein:
-said at most two metals M are chosen from a first subgroup of metals consisting of: nb, V, Fe, the atomic fraction c being the sum of the atomic fractions of the metals M,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.30 and 0.38 inclusive,
c is between 0.09 and 0.20, inclusive,
-d is between 0.001 and 0.03 inclusive.
5. The outer member (1) according to claim 4, wherein said metallic trace elements T are selected from a first subgroup of trace elements 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 said metal M incorporated In said alloy.
6. The external member (1) according to claim 4, wherein said metallic trace elements T are selected from a second subgroup of trace elements comprising Nb, V, Fe, Ru, Rh, Au, Pt, Cr, B, with the exception of said metal M incorporated in said alloy.
7. The outer member (1) according to claim 6, wherein:
-said at most two metals M are selected from a second subgroup of metals consisting of: nb, Fe, the atomic fraction c being the sum of the atomic fractions of the metals M,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.30 and 0.38 inclusive,
c is between 0.09 and 0.19 inclusive,
-d is between 0.001 and 0.03 inclusive.
8. The outer member (1) according to claim 7, wherein:
-said alloy comprises a single said metal M consisting of iron,
said alloy conforming to the atomic formula TiaPdbFecTd，
And the metallic trace element T is selected from a third subgroup of trace elements comprising Nb, V, Ru, Rh, Au, Pt, Cr, B,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.31 and 0.35 inclusive,
c is between 0.11 and 0.19 inclusive,
-d is between 0.001 and 0.03 inclusive.
9. The outer member (1) according to claim 7, wherein:
-said alloy comprises a single said metal M consisting of niobium,
said alloy conforming to the atomic formula TiaPdbNbcTd，
And said metallic trace element T is selected from a fourth subgroup of trace elements consisting of V, Fe, Ru, Rh, Au, Pt, Cr, B,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.34 and 0.38 inclusive,
c is between 0.09 and 0.16, inclusive,
-d is between 0.001 and 0.03 inclusive.
10. The outer member (1) according to claim 8, wherein the alloy contains at most two metallic trace elements T selected from chromium and boron, and wherein the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.31 and 0.33 inclusive,
c is between 0.14 and 0.19 inclusive,
d is between 0.010 and 0.030, inclusive.
11. The external component (1) according to claim 9, wherein the alloy contains at most two metallic trace elements T selected from chromium and boron, and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.34 and 0.36, inclusive,
c is between 0.11 and 0.15 inclusive,
d is between 0.010 and 0.030, inclusive.
12. The outer member (1) according to claim 1, wherein the mass content of palladium is less than or equal to 55.0% of the total alloy.
13. The outer member (1) according to claim 12, wherein the mass content of palladium is less than or equal to 52.5% of the total alloy.
14. The outer member (1) according to claim 13, wherein the mass content of palladium is less than or equal to 51.0% of the total alloy.
15. A timepiece (10) or piece of jewelry comprising at least one external member (1) according to claim 1.
Claims (18)
1. An exterior part (1) for a timepiece or jewelry, made of a light noble metal alloy comprising titanium and palladium, characterized in that said alloy conforms to the atomic formula TiaPdbMcTd，
Wherein a, b, c, d are the aggregate atomic fractions such that a + b + c + d =1,
wherein:
a is between 0.44 and 0.55 inclusive,
b is between 0.30 and 0.45 inclusive,
c is between 0.04 and 0.24 inclusive,
-d is between 0.001 and 0.03 inclusive,
-wherein the alloy comprises at most two metals M selected from the main group of metals consisting of: nb, V, Fe, Co, Au, Pt, the atomic fraction c being the sum of the atomic fractions of the metals M,
-wherein the atomic fraction d is the sum of the atomic fractions of metallic microelements T, each of said metallic microelements T being chosen In an atomic proportion of less than 3.0% of the total alloy, said metallic microelements T being chosen from a main group of microelements consisting of 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 said metal M incorporated In said alloy, said alloy containing at least 0.05% of boron,
-100% of the remaining atoms consist of the at most two metals M,
-and the alloy comprises at least 50% by mass of palladium.
2. The outer member (1) according to claim 1, wherein the alloy contains less than 0.3 atomic% boron.
3. The outer member (1) according to claim 1 or 2, wherein the atomic fractions a, b, c, d are such that:
a is between 0.48 and 0.52 inclusive,
b is between 0.30 and 0.43 inclusive,
c is between 0.05 and 0.21 inclusive,
-d is between 0.001 and 0.03 inclusive.
4. The outer member (1) according to claim 3, wherein:
-said at most two metals M are chosen from a first subgroup of metals consisting of: nb, V, Fe, the atomic fraction c being the sum of the atomic fractions of the metals M,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.30 and 0.38 inclusive,
c is between 0.09 and 0.20, inclusive,
-d is between 0.001 and 0.03 inclusive.
5. The outer member (1) according to claim 4, wherein said metallic trace elements T are selected from a first subgroup of trace elements 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 said metal M incorporated In said alloy.
6. The external member (1) according to claim 4, wherein said metallic trace elements T are selected from a second subgroup of trace elements comprising Nb, V, Fe, Ru, Rh, Au, Pt, Cr, B, with the exception of said metal M incorporated in said alloy.
7. The outer member (1) according to claim 6, wherein:
-said at most two metals M are selected from a second subgroup of metals consisting of: nb, Fe, the atomic fraction c being the sum of the atomic fractions of the metals M,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.30 and 0.38 inclusive,
c is between 0.09 and 0.19 inclusive,
-d is between 0.001 and 0.03 inclusive.
8. The outer member (1) according to claim 7, wherein:
-said alloy comprises a single said metal M consisting of iron,
said alloy conforming to the atomic formula TiaPdbFecTd，
And the metallic trace element T is selected from a third subgroup of trace elements comprising Nb, V, Ru, Rh, Au, Pt, Cr, B,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.31 and 0.35 inclusive,
c is between 0.11 and 0.19 inclusive,
-d is between 0.001 and 0.03 inclusive.
9. The outer member (1) according to claim 7, wherein:
-said alloy comprises a single said metal M consisting of niobium,
said alloy conforming to the atomic formula TiaPdbNbcTd，
And said metallic trace element T is selected from a fourth subgroup of trace elements consisting of V, Fe, Ru, Rh, Au, Pt, Cr, B,
and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.34 and 0.38 inclusive,
c is between 0.09 and 0.16, inclusive,
-d is between 0.001 and 0.03 inclusive.
10. The outer member (1) according to claim 8, wherein the alloy contains at most two metallic trace elements T selected from chromium and boron, and wherein the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.31 and 0.33 inclusive,
c is between 0.14 and 0.19 inclusive,
d is between 0.010 and 0.030, inclusive.
11. The external component (1) according to claim 10, wherein said alloy comprises a single said metallic trace element T consisting of chromium, said alloy conforming to the atomic formula TiaPdbFecCrd。
12. The external component (1) according to claim 9, wherein the alloy contains at most two metallic trace elements T selected from chromium and boron, and the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.34 and 0.36, inclusive,
c is between 0.11 and 0.15 inclusive,
d is between 0.010 and 0.030, inclusive.
13. The external component (1) according to claim 9, wherein said alloy comprises a single said metallic trace element T consisting of chromium, said alloy conforming to the atomic formula TiaPdbNbcCrd，
And the atomic fractions a, b, c, d are such that:
a is between 0.49 and 0.51, inclusive,
b is between 0.34 and 0.36, inclusive,
c is between 0.11 and 0.15 inclusive,
d is between 0.010 and 0.030, inclusive.
14. The outer member (1) according to any one of claims 1 to 13, wherein the palladium content by mass is less than or equal to 60.0% of the total alloy.
15. The outer member (1) according to claim 14, wherein the mass content of palladium is less than or equal to 55.0% of the total alloy.
16. The outer member (1) according to claim 15, wherein the mass content of palladium is less than or equal to 52.5% of the total alloy.
17. The outer member (1) according to claim 16, wherein the mass content of palladium is less than or equal to 51.0% of the total alloy.
18. A timepiece (10) or piece of jewelry comprising at least one external member (1) according to any one of the preceding claims.
Applications Claiming Priority (3)
| 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 |
| EP14200381.3 | 2014-12-29 | ||
| 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 |
|---|---|
| HK1243743A1 true HK1243743A1 (en) | 2018-07-20 |
| HK1243743B HK1243743B (en) | 2020-03-20 |
Family
ID=52130164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HK18103140.3A HK1243743B (en) | 2014-12-29 | 2015-12-17 | Timepiece or jewellery item made from lightweight precious alloy comprising titanium |
Country Status (6)
| Country | Link |
|---|---|
| US (2) | US10136708B2 (en) |
| EP (3) | EP3040790A1 (en) |
| JP (2) | JP6514354B2 (en) |
| CN (2) | CN107208187B (en) |
| HK (1) | HK1243743B (en) |
| WO (2) | WO2016107755A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3572549A1 (en) | 2018-05-24 | 2019-11-27 | Richemont International S.A. | Jewellery item |
| EP3575421B1 (en) * | 2018-06-01 | 2022-09-14 | Omega SA | Piece of watchmaking or jewellery made of an alloy based on gold |
| CN109881044B (en) * | 2019-04-11 | 2021-07-27 | 福建工程学院 | A kind of high-hardness and high-wear-resistant titanium alloy and its preparation method and application |
| 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 | A kind of solder and its preparation method and brazing method |
| CN116987926B (en) * | 2023-08-09 | 2025-10-28 | 深圳市熠辉金珠宝有限公司 | K gold spring and preparation method thereof |
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| GB876887A (en) | 1957-07-12 | 1961-09-06 | Degussa | Gold alloys, for use as material for electric resistances |
| US4851058A (en) * | 1982-09-03 | 1989-07-25 | General Motors Corporation | High energy product rare earth-iron magnet alloys |
| JPS62211334A (en) | 1986-03-12 | 1987-09-17 | Sumitomo Electric Ind Ltd | Functional alloy and its manufacturing method |
| EP0267318A3 (en) * | 1986-11-13 | 1989-01-11 | C. HAFNER GmbH & Co. | Alloy for ornamental purposes |
| JPH02225655A (en) * | 1989-02-28 | 1990-09-07 | Agency Of Ind Science & Technol | Gold alloy that is colored shiny black and its coloring method |
| JPH03110046A (en) * | 1989-09-26 | 1991-05-10 | Tokin Corp | Alloy fine wire and production thereof |
| JPH06145843A (en) * | 1992-11-10 | 1994-05-27 | Tokin Corp | Burn-in test element and burn-in tester |
| DE4306542A1 (en) | 1993-01-14 | 1994-07-21 | Sunder Plassmann Paul Dr | Gold@-titanium@ alloys used for dental restoration work |
| TW360716B (en) * | 1993-02-19 | 1999-06-11 | Citizen Watch Co Ltd | Golden decorative part and process for producing the same |
| US5617377A (en) * | 1995-12-13 | 1997-04-01 | Perret, Jr.; Gerard A. | Watchband connector pin utilizing shape memory material |
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| US6675610B2 (en) * | 1999-12-23 | 2004-01-13 | Guy Beard | Jewelry including shape memory alloy elements |
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| GB0419062D0 (en) * | 2004-08-27 | 2004-09-29 | Johnson Matthey Plc | Platinum alloy catalyst |
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2014
- 2014-12-29 EP EP14200381.3A patent/EP3040790A1/en not_active Withdrawn
-
2015
- 2015-12-17 WO PCT/EP2015/080270 patent/WO2016107755A1/en not_active Ceased
- 2015-12-17 CN CN201580071445.1A patent/CN107208187B/en active Active
- 2015-12-17 US US15/308,185 patent/US10136708B2/en active Active
- 2015-12-17 CN CN201580028804.5A patent/CN106460094B/en active Active
- 2015-12-17 WO PCT/EP2015/080211 patent/WO2016107752A1/en not_active Ceased
- 2015-12-17 EP EP15810677.3A patent/EP3241078B1/en active Active
- 2015-12-17 US US15/533,471 patent/US10206465B2/en active Active
- 2015-12-17 JP JP2017546041A patent/JP6514354B2/en active Active
- 2015-12-17 EP EP15817229.6A patent/EP3240915B1/en active Active
- 2015-12-17 JP JP2017507083A patent/JP6389561B2/en active Active
- 2015-12-17 HK HK18103140.3A patent/HK1243743B/en unknown
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