FIELD OF THE INVENTION
[0001] The invention relates to an alloy based on gold and titanium. This alloy exhibits
enhanced corrosion and color change properties. It can be used in horology or jewelry.
BACKGROUND OF THE INVENTION
[0002] Due to their properties, such as hardness or tensile strength, gold-titanium based
alloys are commonly used in fields such as dentistry, ceramics, horology or jewelry.
[0003] For instance,
WO 2008/018109 discloses an alloy comprising 25-75 wt% of gold and titanium, as well as 0-40 wt%
of nickel.
[0004] Ti
3Au (in mole fraction) exhibits hardness values above most steels and approximately
four times those of titanium.
[0005] WO 2018/162745 discloses a material having a thin layer of Ti
1-xAu
x, in which the atomic fraction x is from 0.22 to 0.28, for instance 0.25 as in Ti
3Au.
[0006] However, specific applications, for instance horology or jewelry, require alloys
having a greater gold fraction than in Ti
3Au (molar fraction).
[0007] For instance,
WO 2016/107755 discloses an alloy comprising at least 750 wt% (≥ 18 carats) of gold. This alloy
is made of:
- 41 to 49.5 at% Au
- 45 to 55 at% Ti
- 2.5 to 13 at% Nb, V, Pd, Pt, Fe
- 0.1 to 2.5 at% at least one of Nb, V, Pd, Pt, Fe, Mo, Ta, W, Co, Ni, Ru, Rh, Ir, Cr,
Mn, Cu, Zn, Ag, Al, B, Si, Ge, Sn, Sb, In.
[0008] In addition to gold and titanium, this alloy comprises at least two alloying elements,
as in Au
0.427Ti
0.50Fe
0.072B
0.001 (in mole fraction) i.e., by weight, Au
750Ti
213Fe
36B
1, in which the total amount of iron and boron represents 37 ‰ by weight vs gold and
titanium.
[0011] US 5,853,661 discloses biocompatible gold alloys comprising 91 to 99.4 wt% gold and 0.5 to 3 wt%
titanium and/or tantalum.
[0012] WO 2010/027329 discloses colored gold alloys comprising more than 10 wt% titanium. Examples include
alloys comprising at least 0.5 wt% (5000 ppm) iron or cobalt.
[0013] Even though some of the above alloys may be used in jewelry or horology, there is
still an interest in improving the properties of gold alloys, especially their resistance
to color change even when exposed to corrosive conditions. The invention relates to
a gold-titanium alloy having these properties.
SUMMARY OF THE INVENTION
[0014] The invention relates to an alloy (three main elements) having improved properties
due to the combination of specific elements. This alloy exhibits improved color change
resistance (i.e. a better tarnishing behavior) especially when exposed to a corrosive
environment. This improvement results from the presence of a specific alloying element
(Pd, Cr, V) in addition to gold and titanium.
[0015] More specifically, the invention relates to an alloy of formula Au
xTi
yM
1zM
2j, wherein:
x = 675 to 805 parts by weight,
y = 190 to 245 parts by weight,
z = 5 to 60 parts by weight,
j = 0 to 20 parts by weight,
x + y + z + j = 1000 parts by weight,
wherein M1 is selected from the group consisting of palladium, chromium, vanadium and mixtures
thereof,
wherein M2 is selected from the group consisting of iron, manganese, and mixtures thereof.
[0016] Formula Au
xTi
yM
1zM
2j also includes: Au
xTi
yM
1z (j = 0); Au
xTi
yM
1zM
2jR (R is a grain-refining element) and Au
xTi
yM
1zR (j = 0; R is a grain-refining element).
[0017] M
1 is preferably palladium.
[0018] When j = 0, the alloy is of formula Au
xTi
yM
1z, wherein:
y = 190 to 245 parts by weight,
z = 5 to 60 parts by weight,
x + y + z = 1000 parts by weight.
[0019] During the preparation of the alloy, a grain-refining element can be incorporated.
This grain-refining element advantageously represents 0 to 2000 ppm, preferably from
30 to 2000 ppm, more preferably from 30 to 1000 ppm, by mass relative to the total
mass of gold, Ti, M
1 and M
2. A grain-refining element is not an alloying element.
[0020] Preferably, the alloy consists of "gold, titanium, M
1, optionally M
2", and includes 0 to 2000 ppm of a grain-refining element R, preferably from 30 to
2000 ppm, more preferably from 30 to 1000 ppm.
[0021] The grain-refining element R is preferably selected from the group consisting of:
- iridium,
- ruthenium,
- boron,
- vanadium, when M1 is not vanadium,
- iron, when M2 is not iron,
- cobalt,
- barium,
yttrium,
- zirconium
- and mixtures thereof.
[0022] The grain-refining element R is preferably selected from the group consisting of:
iridium, ruthenium, boron, cobalt, barium, yttrium, zirconium, and mixtures thereof.
More preferably, the grain-refining element is selected from the group consisting
of: iridium, ruthenium, and mixtures thereof.
[0023] The amount of grain refiner is preferably 30 to 200 ppm by weight with respect to
the total amount of gold, titanium, M
1 and M
2, for instance 50 to 150 ppm.
[0024] The alloying element M
1 (Pd, Cr, V and mixtures thereof) allows increasing the resistance to color change.
[0025] The alloying element M
2 (Fe, Mn, and mixtures thereof) allows increasing the hardness.
[0026] All ranges include the end-points. For instance, the
"675 to 805" and
"between 675 and 805" ranges include the 675 and 805 values.
[0027] In the alloy of formula Au
xTi
yM
1zM
2j, the amount x of gold ranges from 675 to 815 parts by weight, for instance from 740
to 815 or from 750 to 815 parts by weight. It preferably ranges from 750 to 770 parts
by weight.
[0028] In the alloy of formula Au
xTi
yM
1zM
2j, the amount y of titanium ranges from 190 to 245 parts by weight. It preferably ranges
from 190 to 240 parts by weight, more preferably from 200 to 220 parts by weight.
[0029] For instance, in parts by weight, x can range from 750 to 760, y from more than 200
to 220, z from 5 to 50 and j from 0 to 20, with 240 ≤ y + j ≤ 250 and x + y + j =
1000.
[0030] According to a specific embodiment, the alloy has any one of the following formula
(in weight fraction): Au
750-815Ti
200-220M
15-50M
20-20, Au
750-815Ti
200-220M
15-50M
20-20R
10-200ppm, wherein the amount of grain refiner R ranges from 10 to 200 ppm by weight of the
total amount of "gold, titanium, M
1 and M
2".
[0031] According to a particular embodiment of the invention, the alloy has a molar ratio
gold/titanium of from 42.17/57.83 (18 carats, based on the weight of "gold, titanium,
M
1 and M
2") to less than 54.86/45.14 (20 carats).
[0032] When x varies from 675 to 805, the amount of gold approximately ranges from more
than 16 to less than 20 carats as compared to the total amount of "gold, titanium,
M
1 and M
2".
[0033] The alloy may comprise impurities. In general, impurities may result from the metals
used to form the alloy. Advantageously, these possible impurities amount to a total
of less than 1000 ppm, more preferably, less than 500 ppm, more preferably less than
250 ppm, by weight of the alloy (x + y + z + j). The alloy may comprise a total amount
of impurities of less than 100 ppm.
[0034] Accordingly, the alloy may comprise more impurities than grain refiner. The benefit
resulting from the presence of a grain refiner is greater than any negative effect
that might result from the presence of impurities, even when the amount of impurities
exceeds that of grain refiner.
[0035] In particular, impurities can include any one or more of carbon, oxygen and nitrogen.
In general, the amount of oxygen may be greater than that of nitrogen, which may be
greater than that of carbon.
[0036] The total amount of one or more of carbon, oxygen and nitrogen is preferably less
than 1000 ppm, more preferably, less than 500 ppm, more preferably less than 300 ppm
even more preferably less than 250 ppm, by weight of the alloy (x + y + z + j). However,
in some cases, the total amount of one or more of oxygen and nitrogen may amount to
more than 1000 ppm, preferably less than 10 000 ppm, more preferably less than 7500
ppm, even more preferably less than 5000 ppm. This large amount of oxygen and/or nitrogen
may result from the process for preparing the alloy, in particular if the melted/solubilized
Au, Ti, M
1, M
2 and R (M
2 and R are optional) elements are more or less slightly exposed to air. Experimental
conditions may therefore impact the amount of impurities such as oxygen, carbon and
nitrogen; however, in general, metal or metalloid impurities result from the Au, Ti,
M
1, M
2 and M (M
2 and R are optional) materials used to prepare the alloy.
[0037] The total amount of impurities other than carbon, nitrogen and oxygen is preferably
less than 500 ppm, more preferably less than 250 ppm, even more preferably less than
230 ppm, by weight of the alloy (x + y + z + j). These other impurities may include
but not limited to hydrogen, sulfur; silicon; phosphorous; selenium; halogens; metals
other than gold, titanium, M
1, M
2 and R; metalloids other than the grain refiner R.
[0038] According to a preferred embodiment, non-metallic and non-metalloid impurities represent
less than less than 1000 ppm, more preferably, less than 500 ppm, more preferably
less than 300 ppm even more preferably less than 250 ppm) while metallic impurities
(metals other than gold, titanium, M
1, M
2 and R; metalloids other than the grain refiner R) preferably represent less than
500 ppm, more preferably less than 100 ppm, even more preferably less than 50 ppm,
by weight of the alloy (x + y + z + j).
[0039] The Au
xTi
yM
1zM
2j alloy has a grain size that preferably ranges from 10 to 300 µm, more preferably
from 5 to 100 µm.
[0040] The Au
xTi
yM
1zM
2j alloy preferably comprises between 0 and 50 % by volume of Ti
3Au (molar fraction) precipitates (Ti
3Au or Ti
42.17Au
57.83 by weight).
[0041] Formula Ti
3Au corresponds to an alloy consisting of gold and titanium, wherein the molar ratio
gold/titanium is 1/3. All other formulas, for instance Au
xTi
yM
1zM
2j, Au
xTi
yM
1zM
2jR or Au
xTi
yM
1z, are in weight.
[0042] Ti
3Au precipitates can be formed during a final heat treatment to improve the hardness
of the alloy.
[0043] These Ti
3Au precipitates are dispersed within the Au
xTi
yM
1zM
2j matrix.
[0044] The alloy has a hardness that preferably ranges from 200 to 650 Hv, more preferably
from 400 to 650 Hv, for instance from 40 to 500 Hv after a hardening heat treatment.
[0045] Due to its hardness properties, the alloy resists to scratches. In addition, the
grain refiner, improves the aesthetic properties of the alloy.
[0046] It also exhibits improved resistance to corrosion and has reduced color change properties.
[0047] The present invention also relates to a process for preparing the alloy of formula
Au
xTi
yM
1zM
2j. This process comprises the following steps:
- 1/ preparing a material of formula AuxTiyM1zM2j from x parts by weight of gold, y parts by weight of titanium, z parts by weight
of M1, j parts by weight of M2 and 0 to 2000 ppm of a grain refining element R,
wherein x = 675 to 805 parts by weight, y = 190 to 245 parts by weight,
wherein x + y + z + j = 1000,
wherein M1 is selected from the group consisting of palladium, chromium, vanadium and mixtures
thereof,
wherein M2 is selected from the group consisting of iron, manganese, and mixtures thereof,
- 2/ optionally, homogenizing the resulting material of formula AuxTiyM1zM2j, which comprises 0 to 2000 ppm of a grain refining element R,
- 3/ optionally, deformation of the material from step 2/,
- 4/ optionally, annealing the material from step 3/,
- 5/ optionally, precipitation by thermal treatment of the material from step 2/,3/
or 4/ and obtaining an alloy of formula AuxTiyM1zM2j, which comprises 0 to 2000 ppm of a grain refining element R.
[0048] Step 1/ is an alloying step, which is preferably carried out by casting or from powder
technology. It can involve mixing powders of pure elements or powder(s) of pre-alloyed
elements.
[0049] The powder technology includes any technique selected from the group consisting of:
metal injection, selective melting and powder fusion.
[0050] The metal injection preferably includes a sintering step while the selective melting
and the powder fusion preferably include localized melting by laser or electron beam.
[0051] The powder technology is preferably any one selected from the group consisting of:
MIM-like (metal injection molding-like), spark plasma sintering (SPS), binder jetting,
material extrusion, material jetting, sheet lamination, vat photopolymerization, powder
bed fusion (for instance LPBF i.e. laser powder bed fusion), selective laser melting
(SLM), direct energy deposition and hot pressing.
[0052] It is preferably a laser or electron beam assisted additive manufacturing step.
[0053] It is preferably a selective melting technique, more preferably a selective laser
melting (SLM) technique.
[0054] Step 1/ preferably consists in melting/solubilizing the Au, Ti, M
1, M
2 and R elements (M
2 and R are optional) at a temperature T
PREP that may be greater than that of the respective melting points of these elements
(or mixtures thereof) and below that of their (or mixtures thereof) respective boiling
points. For instance, alloying gold, titanium and iridium may be carried out at a
temperature of more than 1500°C (melting point of the alloy) and less than 2856°C
(boiling point of gold). The temperature T
PREP may be below the melting point of Ti or R. It is preferably above the melting point
of gold. Melted gold can then solubilize one or more of: titanium, M
1, M
2, grain refiner R.
[0055] The alloying step 1/ may include making a pre-alloy or pure elements. It may involve
using powder(s) or bulk piece(s). Making a pre-alloy allows a lower casting temperature.
If used, the pre-alloying step is preferably carried out in an arc furnace.
[0056] In general, pre-alloying or casting (without pre-alloying) the alloy, in particular
in an arc furnace, is carried out at a temperature that preferably ranges from 1500
to 2850°C, more preferably from 1500 to 2700°C. In that case, the different elements
of the alloy are preferably maintained at this temperature for 5 seconds to 30 minutes,
for instance for 5 seconds to 20 minutes. For instance, it can last from 5 seconds
to 5 minutes, more preferably for 10 seconds to 2 minutes.
[0057] Casting the different elements of the alloy can consist in casting the appropriate
amounts of elements by any means, for instance any one of: arc furnace, induction
furnace, cold crucible induction melting...
[0058] The grain refiner may also act as seeding material for the Au
xTi
yM
1zM
2j alloy as the material resulting from step 1/ has an improved microstructure as compared
to alloys consisting of gold and titanium. While thermal treatments increase the grain
size, the grain refiner counterbalances this effect by slowing down the grain's growth.
[0059] According to a preferred embodiment, the homogenizing step 2/ is carried out at a
temperature, T
HOM, of from 1200 to 1400°C, more preferably between 1250 and 1350°C.
[0060] The homogenizing step 2/ is optional. The skilled person in the art is able to consider
if a homogenizing step should be carried out on the material resulting of step 1/,
for instance depending on the size of the cast or if it has been prepared from powder(s).
[0061] The homogenizing step 2/ is preferably carried out for 10 minutes to 12 hours, more
preferably for 30 minutes to 8 hours, for instance for 1 hour to 2 hours.
[0062] For instance, homogenizing step 2/ may be carried out between 1250 and 1350°C, for
1 hour to 2 hours.
[0063] The process preferably includes a cooling stage between steps 2/ and 3/. The homogenized
material is preferably rapidly cooled, by air quenching or water quenching, more preferably
by air quenching.
[0064] Deforming step 3/ is preferably carried out by cold compression or by rolling compression
or by hot forging, more preferably by hot forging. The deformation is preferably comprised
between 20 and 80%, more preferably between 30 and 70%.
[0065] The deforming step is preferably carried out at a temperature T
DEF of between 500 and 1300°C, more preferably between 700 and 1200°C.
[0066] According to a preferred embodiment, the annealing step 4/ is carried out at a temperature,
T
ANN, of from 1100 to 1400°C, more preferably between 1250 and 1350°C.
[0067] Annealing step 4/ is preferably carried out for 5 minutes to 12 hours, more preferably
for 10 minutes to 4 hours, for instance for 10 minutes to 2 hours.
[0068] For instance, annealing step 4/ may be carried out between 1250 and 1350°C, for 10
minutes to 2 hours.
[0069] Precipitation step 5/ is preferably carried out at a temperature T
PRECIP of from 400 to 1000°C, more preferably between 500°C and 900°C, for instance between
600°C and 900°C.
[0070] At least one of steps 1/ to 5/ may be followed by a cooling stage to room temperature.
Steps 1/ to 5/ are preferably followed by a fast cooling stage to room temperature,
preferably by water or air quenching.
[0071] In general, T
PREP is greater than T
HOM, which is greater than T
DEF. On the other hand, T
PRECIP is generally smaller than T
HOM.
[0072] The present invention also relates to an item comprising or consisting of the alloy
of formula Au
xTi
yM
1zM
2j. Accordingly, this alloy can be used in order to manufacture luxury goods.
[0073] For instance, it may be a watch component comprising (or consisting of) the alloy.
It may be a jewel comprising (or consisting of) the alloy.
[0074] The item comprising or consisting of the alloy of formula Au
xTi
yM
1zM
2j can be a jewel, a leather good, or a clothing accessory. It may also be a watch,
a writing accessory, or a decorative item. For instance, it can be any of the followings:
ring, ear ring, necklace, bracelet, pendant, watch or watch movement component (case,
bezel, case back, crown, other case small parts, balance wheel, gear wheel, axis,
screw...), buckle (belt, purse...), tie bar, cuff links, money clip, hair pin, pen,
paper knife...
[0075] The alloy according to the invention can therefore be used in a field selected from
the group consisting of: jewelry, horology, clothing, writing accessories, leather
goods, and ornaments.
[0076] The invention and its advantages will become more apparent to one skilled in the
art from the following figures and examples.
BRIEF DESCRIPTION OF THE DRAWINGS
[0077] Figure 1 shows the resistance to color change (tarnishing behavior) of the gold titanium
alloys over time.
EXAMPLES
[0078] Alloys of formula Au
xTi
yM
1zM
2j have been prepared following different experimental conditions, as outlined in Table
1. Samples "INV" refer to alloys according to the invention while samples "REF" are
reference examples.
[0079] The process for preparing the different alloys comprises the following steps:
- 1/ Preparing a material: melting the appropriate amounts of gold, titanium, M1 and R elements, in an arc furnace, between 1500°C and 2856°C.
- 2/ Homogenizing the resulting material.
| Composition |
State |
| Au750Ti249.95-Ir0.05 (REF-1) |
Homogenized 1300°C 5hours |
| Au750T1219.95Cr30-Ir0.05 (INV-1) |
Homogenized 1300°C 5hours |
| Au750Ti219.95Al30-Ir0.05 (REF-2) |
Homogenized 1100°C 1.5hours |
| Au750Ti219.95Pd30-Ir0.05 (INV-2) |
Homogenized 1300°C 5hours |
| Au750Ti207.5V40-Ir2.5 (INV-3) |
Homogenized 1300°C 5hours |
Table 1: Experimental conditions for the preparation of Au
xTi
yM
1zM
2j alloys.
| Alloy (AuxTiyM1zM2j) |
ΔE (14 days) |
ΔE (31 days) |
ΔE (44days) |
ΔE (71days) |
ΔE (100days) |
| AuTi (REF-1) |
0 |
3.1 |
3.6 |
4.2 |
4 |
| AuTiCr (INV-1) |
2.4 (21d) |
|
2.8 |
|
|
| AuTiAl (REF-2) |
1.1 |
1.1 |
1.3 |
1.2 |
1.2 |
| AuTiPd (INV-2) |
1.2 |
1.3 |
1.2 |
1.5 |
1.3 |
| AuTiV (INV-3) |
1.2 (21d) |
|
2.4 |
|
|
[0080] Table 2 and figure 1 show that alloys according to the invention afford improved
color change resistance when alloys are exposed to a corrosive environment according
to the Tuccillo-Nielsen test.
Tuccillo-Nielsen Test
[0081] The Tuccillo-Nielsen test has been carried out in order to evaluate the degradation
behavior (corrosion) of the alloys of Table 1 at the material-electrolyte interface,
by a cyclic immersion system.
[0082] The equipment consists of two carrying wheels, holding the samples (alloys), which
are in a continuous rotation, at a speed of 1 rpm, so the samples alternately pass
from a liquid medium to a gaseous medium. The equipment tanks are connected to a thermostat
with external recirculation, so as to maintain a constant temperature of no more than
37°C, during testing.
[0083] The electrolyte used is artificial sweat according to the EN 1811 standard with buffered
pH at 6.50. Throughout the test, the pH is adjusted to remain at 6.50±0.2 by adding
HCl or NaOH. The tested samples are embedded in cold resin and polished (1 µm grain).
Then, the samples are fixed to the ends of the wheel by plastic screws. Throughout
the test, degradation is monitored by color measurement according to ISO 8654 and
by taking photos or by optical microscopy.
1. Alloy of formula Au
xTi
yM
1zM
2j in which:
x = 675 to 805 parts by weight,
y = 190 to 245 parts by weight,
z = 5 to 60 parts by weight,
j = 0 to 20 parts by weight,
x + y + z + j = 1000 parts by weight,
wherein M1 is selected from the group consisting of palladium, chromium, vanadium and mixtures
thereof,
wherein M2 is selected from the group consisting of iron, manganese, and mixtures thereof.
2. Alloy according to claim 1, wherein M1 is palladium.
3. Alloy according to any one of claims 1 to 2, wherein:
j = 0,
y = 190 to 245 parts by weight,
z = 5 to 60 parts by weight,
x + y + z = 1000 parts by weight.
4. Alloy according to any one of claims 1 to 3, wherein the amount x of gold ranges from
750 to 815 parts by weight.
5. Alloy according to any one of claims 1 to 4, wherein the alloy includes 30 to 2000
ppm of a grain-refining element R, by mass relative to the total mass of gold, Ti,
M1 and M2,
wherein the grain-refining element R is selected from the group consisting of: iridium,
ruthenium, boron, vanadium, when M1 is not vanadium, iron, when M2 is not iron, cobalt, barium, yttrium, zirconium, and mixtures thereof.
6. Process for preparing the alloy of formula Au
xTi
yM
1zM
2j according to any one of claims 1 to 5, wherein the process comprises the following
steps:
1/ preparing a material of formula AuxTiyM1zM2j from x parts by weight of gold, y parts by weight of titanium, z parts by weight
of M1, j parts by weight of M2 and 0 to 2000 ppm of a grain refining element R,
wherein x = 675 to 805 parts by weight, y = 190 to 245 parts by weight,
wherein x + y + z + j = 1000,
wherein M1 is selected from the group consisting of palladium, chromium, vanadium and mixtures
thereof,
wherein M2 is selected from the group consisting of iron, manganese, and mixtures thereof,
2/ optionally, homogenizing the resulting material of formula AuxTiyM1zM2j.
3/ optionally, deformation of the material from step 2/,
4/ optionally, annealing the material from step 2 or 3/,
5/ optionally, precipitation by thermal treatment of the material from step 2/, 3/
or 4/ and obtaining an alloy of formula AuxTiyM1zM2j.
7. Process according to claim 6, wherein homogenizing step 2/ is carried out at a temperature
of from 1200°C to 1400°C, for 10 minutes to 12 hours, preferably between 1250°C and
1350°C for 1 hour to 2 hours.
8. Process according to any one of claims 6 to 7, wherein the process comprises a deforming
step 3/, which is carried out by any one of: cold compression, hot forging, or rolling
compression.
9. Process according to any one of claims 6 to 8, wherein the process includes a step
4/ of annealing the material from step 2 or 3/.
10. Process according to claim 9, wherein step 4/ of annealing is carried out at a temperature
of from 1100 to 1400°C for 5 minutes to 12 hours, preferably between 1250 and 1350°C,
for 10 minutes to 2 hours.
11. Process according to any one of claims 6 to 10, wherein the process comprises a precipitation
step 5/, which is carried out at a temperature of from 400°C to 1000°C.
12. Process according to any one of claims 6 to 11, wherein the process comprises steps
1/ to 5/, wherein each one of steps 1/ to 5/ is followed by a water quenching step.
13. Watch component comprising the alloy of any one of claims 1 to 5.
14. Jewel comprising the alloy of any one of claims 1 to 5.
15. Use of the alloy of any one of claims 1 to 5, in a field selected from the group consisting
of: jewelry, horology, clothing, writing accessories, leather goods, and ornaments.