EP4274916A1 - Gold- und titanbasierte legierung - Google Patents
Gold- und titanbasierte legierungInfo
- Publication number
- EP4274916A1 EP4274916A1 EP22700363.9A EP22700363A EP4274916A1 EP 4274916 A1 EP4274916 A1 EP 4274916A1 EP 22700363 A EP22700363 A EP 22700363A EP 4274916 A1 EP4274916 A1 EP 4274916A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloy
- weight
- ppm
- parts
- gold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 122
- 239000000956 alloy Substances 0.000 title claims abstract description 122
- 239000010931 gold Substances 0.000 title claims abstract description 82
- 239000010936 titanium Substances 0.000 title claims abstract description 77
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 42
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 15
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 bore Chemical compound 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 239000010437 gem Substances 0.000 claims abstract description 4
- 229910001751 gemstone Inorganic materials 0.000 claims abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000001556 precipitation Methods 0.000 claims description 20
- 238000005266 casting Methods 0.000 claims description 19
- 238000010791 quenching Methods 0.000 claims description 18
- 230000000171 quenching effect Effects 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000007669 thermal treatment Methods 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 230000006835 compression Effects 0.000 claims description 8
- 238000007906 compression Methods 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 238000005242 forging Methods 0.000 claims description 3
- 239000010985 leather Substances 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000003353 gold alloy Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000005275 alloying Methods 0.000 description 7
- ZNKMCMOJCDFGFT-UHFFFAOYSA-N gold titanium Chemical compound [Ti].[Au] ZNKMCMOJCDFGFT-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910001258 titanium gold Inorganic materials 0.000 description 7
- 229910001020 Au alloy Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000003446 memory effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000265 homogenisation Methods 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052752 metalloid Inorganic materials 0.000 description 4
- 150000002738 metalloids Chemical class 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000005097 cold rolling Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000960 colored gold Inorganic materials 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 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
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- 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
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
-
- 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
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
Definitions
- the invention relates to an alloy based on gold and titanium.
- This alloy which also comprises a specific amount of grain refiner, can be used in horology or jewelry.
- BACKGROUND OF THE INVENTION 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.
- WO 2008/018109 discloses an alloy comprising 25-75 wt% of gold and titanium, as well as 0-40 wt% of nickel.
- Ti 3 Au in mole fraction
- WO 2018/162745 discloses a material having a thin layer of Ti 1-x Au x , in which the atomic fraction x is from 0.22 to 0.28, for instance 0.25 as in Ti 3 Au.
- specific applications for instance in horology or jewelry, require alloys having a greater gold fraction than in Ti 3 Au (molar fraction).
- 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.
- this alloy comprises at least two alloying elements, as in Au 0.427 Ti 0.50 Fe 0.072 B 0.001 (in mole fraction) i.e., by weight, Au 750 Ti 213 Fe 36 B 1 , in which the total amount of iron and boron represents 37000 ppm by weight vs gold and titanium.
- Binary Ti1-xAux alloys have been reported (Svanidze, High hardness in the biocompatible intermetallic compound ⁇ -Ti 3 Au, Sci. Adv., 2016, pages 1-6). These binary alloys are high hardness and biocompatible alloys. They are free of any grain refiner.
- the invention relates to an alloy (two or three main elements) having improved properties due to the presence of a small amount of a specific grain refiner. This alloy is easy to shape by mechanical deformation since it exhibits a small shape memory effect, smaller than that of conventional gold-titanium alloys.
- This alloy is therefore free of palladium.
- This alloys consists in gold, titanium, optionally silver and/or aluminum, and one or more grain refiner selected from a specific list of elements.
- the amount of grain refiner is 30 to 200 ppm by weight with respect to the total amount of gold, titanium and M element (Ag and/or Al).
- z is less than 30 ppm by weight of x + y + j, the amount of refiner is too small to afford any refining effect to the alloy.
- z is more than 200 ppm by weight of x + y + j, aggregates form within the alloy. Aggregates can weaken the alloy, lead to the formation of cracks and even aesthetic defects.
- the alloying elements silver and aluminum allow lowering the temperature of transformation of the alloy. They facilitate manufacturing processes of the alloy, for instance shaping, forging, casting.
- the alloy can therefore consists of three elements: gold, titanium and one grain refiner, for instance gold, titanium and iridium.
- the amount z of grain refiner ranges from 30 to 200 ppm by weight when x + y + j is equal to 1000 parts by weight.
- z ranges from 40 to 100 ppm, more preferably from 40 to 60 ppm, even more preferably z is equal to 50 ppm.
- the amount x of gold ranges from 375 to 917 parts by weight, for instance from 580 to 917 or from 750 to 917 parts by weight. It preferably ranges from 580 to 760 parts by weight.
- the amount y of titanium ranges from 83 to 625 parts by weight. It preferably ranges from 240 to 420 parts by weight.
- the alloy has any one of the following formula (in weight fraction): Au 583 Ti 417 R z , Au 753 Ti 247 R z or Au 804 Ti 196 R z , wherein the amount z of grain refiner ranges from 30 to 200 ppm by weight of the total amount of gold and titanium.
- the alloy has a molar ratio gold/titanium of between 25.39/74.61 (14 carats) to 54.86/45.14 (20 carats), more preferably from 42.17/57.83 (18 carats, based on the weight of titanium and gold) to 54.86/45.14 (20 carats).
- the amount of gold approximately ranges from 9 to 22 carats as compared to the total amount of gold and titanium.
- the alloy may comprise impurities. In general, impurities may result from the metals used to form the alloy.
- 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 + j + z).
- the alloy may comprise a total amount of impurities of less than 100 ppm. 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.
- Impurities do not affect the poor (or lack of) shape memory resulting from the presence of 30-200 ppm of grain refiner.
- impurities can include any one or more of carbon, oxygen and nitrogen.
- the amount of oxygen may be greater than that of nitrogen, which may be greater than that of carbon.
- 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 + j + z).
- the total amount of one or more of oxygen and nitrogen may amount to more than 1000 ppm, preferably less than 10000 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 and R elements are more or less slightly exposed to air. Experimental conditions may therefore impact the amount of impurities such as oxygen and nitrogen; however, in general, metal or metalloid impurities result from the Au, Ti, R and M materials used to prepare the alloy.
- 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 + j + z).
- 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, silver, aluminum and the grain refiner 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 + j + z).
- the grain refiner In addition to a smaller grain size of the alloy, the grain refiner also contributes to the control of the precipitation step. A smaller grain size reduces the macroscopic deformation of the alloy. As a result, the grain refiner also improves the ductility of the alloy as its ability to elongate increases as compared to alloys that comprise less than 30 ppm or more than 200 ppm of grain refiner.
- the Au x Ti y R z M j alloy has a grain size that preferably ranges from 10 to 300 ⁇ m, more preferably from 20 to 200 ⁇ m.
- the Au x Ti y R z M j alloy preferably comprises between 10 and 70 % by volume of Ti 3 Au (molar fraction) precipitates (Ti 3 Au or Ti 42.17 Au 57.83 by weight), more preferably between 20 and 60 %.
- Formula Ti 3 Au corresponds to an alloy consisting of gold and titanium, wherein the molar ratio gold/titanium is 1/3. All other formulae, for instance Au x Ti y R z M j or Au x Ti y R z , are in weight.
- Ti 3 Au precipitates actually improves the hardness of the alloy. These Ti 3 Au precipitates are dispersed within the Au x Ti y R z M j matrix. They are located at the interface between the grains i.e.
- the alloy has a hardness that preferably ranges from 220 to 650 Hv, more preferably from 400 to 650 Hv, for instance from 450 to 500 Hv. Due to its hardness properties, the alloy resists to scratches. In addition, the grain refiner, which prevents crack initiation, improves the aesthetic properties of the alloy.
- the present invention also relates to a process for preparing the alloy of formula Au x Ti y R z M j .
- the casting step consists in melting/solubilizing the Au, Ti, M and R elements at a temperature TCAST 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.
- TCAST melting point of Ti or R. It is preferably above the melting point of gold. Melted gold can then solubilize titanium and/or the grain refiner R and/or M.
- the casting step 1/ may include making a pre-alloy.
- the pre-alloying step is preferably carried out in an arc furnace.
- the casting step may be carried out
- the casting conditions (casting temperature and time) can be adjusted.
- 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 2470 to 2850°C, more preferably from 2480 to 2700 °C.
- 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.
- casting the alloy following a pre-alloying step, is carried out at a temperature of 1100 to 1500°C, more preferably from 1250 to 1450°C, in particular in an induction furnace or a cold crucible induction melting.
- the different elements of the alloy are preferably maintained at this temperature for 5min to 60min, for instance for 10min to 30min.
- 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...
- the casting step 1/ is followed by a cooling stage, for instance by air quenching or water quenching, preferably by water quenching.
- the grain refiner may also act as seeding material for the Au x Ti y R z M j alloy as the material resulting from the casting step 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.
- 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.
- the homogenizing step 2/ is preferably carried out for 2 hours to 12 hours, more preferably for 5 hours to 10 hours, for instance for 5 hours to 8 hours.
- homogenizing step 2/ may be carried out between 1250 and 1350°C, for 5 hours to 10 hours.
- 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 water quenching.
- Deforming step 3/ is preferably carried out by cold compression or by rolling compression or by hot forging, more preferably by cold compression.
- the deformation is preferably comprised between 20 and 80%, more preferably between 30 and 70%.
- the deforming step is preferably carried out at a temperature TDEF of between 0 and 50°C, more preferably between 20 and 30°C.
- Precipitation step 4/ is preferably carried out at a temperature TPRE of from 400 to 1000°C, more preferably between 500°C and 700°C, for instance between 500°C and 600°C.
- precipitation step 4/ is preferably carried out for 10 minutes to 300 minutes, more preferably for 30 minutes to 180 minutes, for instance for 30 minutes to 120 minutes.
- precipitation step 4/ is preferably carried out for 1 hour to 15 hours, more preferably for 2 hours to 12 hours. For instance, after deformation step 3/, precipitation step 4/ may be carried out between 500°C and 600°C, for 30 minutes to 2 hours.
- the alloy is cooled to room temperature (20 to 25°C), preferably by air quenching or water quenching, more preferably by water quenching.
- the precipitation step 4/ promotes the formation of a Au x Ti y R z M j matrix comprising Ti 3 Au precipitates, resulting in an improved hardness.
- step 2/ and/or step 4/ may increase the amount of oxygen impurity, which is preferably less than 1000 ppm.
- At least one of steps 1/ to 4/ may be followed by a cooling stage to room temperature. Steps 1/ to 4/ are preferably followed by a cooling stage to room temperature, preferably by water quenching.
- T CAST is greater than T HOM , which is greater than T DEF .
- T PRE is generally greater than T DEF but smaller than T HOM .
- the grain refiner affords smaller grain size.
- the deformation step and the precipitation step improve the hardness of the alloy.
- the present invention also relates to an item comprising or consisting of the alloy of formula Au x Ti y R z M j . Accordingly, this alloy can be used in order to manufacture luxury goods. 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.
- the item comprising or consisting of the alloy of formula Au x Ti y R z M j 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...
- 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.
- Figure 3 shows Ti3Au precipitates in Au 750 Ti 250 Ir 50 ppm (weight fraction).
- Figures 5 and 6 show Ti 3 Au (molar fraction) precipitates in Au 750 Ti 250 Ir 50ppm (weight fraction).
- Figure 7 shows the recovered deformation of gold-titanium alloys (Au 750 Ti 250 and Au 750 Ti 250 Ir 50 ppm) after a cold deformation of 0-15%.
- Figure 8 shows the grain size evolution of gold-titanium alloys (Au 750 Ti 250 and Au 750 Ti 250 Ir 50 ppm).
- the process for preparing the different alloys comprises the following steps: 1/ Casting a material (samples 1-30): melting the appropriate amounts of gold, titanium and, eventually, iridium elements, for instance in an arc furnace, preferably between 2466°C and 2856°C. 2/ Homogenizing the resulting material (samples 6-30). This thermal treatment may be followed by a quenching step, preferably in water. 3/ Optionally, deformation by cold compression (samples 11-12 and 22-30). 4/ Optionally, precipitation by thermal treatment (samples 13-30). This thermal treatment may be followed by a quenching step (preferably in water).
- Table 1 Experimental conditions for the preparation of Au x Ti y R z alloys.
- Y Yes N: No (wq) : water quenching
- Hom homogenization at 1310°C for 7 hours
- Def deformation by cold compression or by cold rolling (sample 25 only)
- PP thermal treatment for precipitation
- Table 1 shows that, depending on the experimental conditions, the alloy according to the invention exhibits a hardness that can range from 227 to 609 Hv. The alloy hardness is improved when the process successively involves a homogenization step, a deformation step and a precipitation step. These steps are preferably following by a quenching step, for instance water quenching.
- Figure 8 shows the grain size evolution of a sample after a homogenization step (1310°C for 7 hours).
- the technical effect resulting from the presence of smaller grains is the reduction of macroscopic deformation that leads to crack initiation.
- the alloy according to the invention exhibits a more homogeneous deformation through the bulk, less segregation, and a better aesthetics since grains cannot be seen at a macroscopic scale.
- figure 1 shows that the amount of grain refiner should be limited to 200 ppm in order to keep the smaller grain size benefit. Additionally, since the grain refiner prevents crack initiation, it also improves the aesthetic properties of the alloy, especially after a polishing step.
- the homogenization step (samples 6-10) may be followed by a quenching step, preferably in water.
- the deformation step preferably by cold compression, improves the hardness of the alloy (samples 11 and 12 vs samples 6 and 8).
- the precipitation step is a thermal treatment, preferably at a temperature of at least 400°C and for 1 hour or more. This thermal treatment may be followed by a quenching step, preferably in water. It promotes the precipitation of Ti 3 Au.
- Ti 3 Au precipitates improves the hardness of the alloy. As compared to Au 750 Ti 250 , the presence of 30-200 ppm of grain refiner promotes the Ti 3 Au precipitation kinetics.
- the deformation step (in the presence of a grain refiner or not) contribute to this phenomenon as well.
- the above precipitation step 4/ promotes a mixed structure of Au-Ti and Ti 3 Au.
- the resulting alloy comprises Ti 3 Au precipitates within a gold-titanium, or gold-titanium-grain refiner, matrix (figures 3-6).
- Figure 7 shows the recovered deformation of different alloys (Au 750 Ti 250 and Au 750 Ti 250 Ir 50 ppm) after an incremental cold deformation of 0-15% and a mild heating step between 450°C and 700°C.
- Step 2/ is a homogenizing step carried out at 1310°C for 7 hours while step 4/ is a precipitation step carried out at 750°C for 10 hours.
- the alloy according to the invention exhibits a recovered deformation of 2% or less vs 3% or more for Au 750 Ti 250 . This is a significant improvement of roughly 33%.
- the recovered deformation relates to the difference between the size of a sample, following an incremental deformation stage (0-15%), and its final size after a mild heating step and the subsequent cooling stage. This incremental deformation is not the deformation of step 3/.
- the mild heating step following the incremental deformation is not a precipitation step 4/.
- This mild heating step allows change from martensitic phase to austenitic phase. If upon cooling, the alloy recovers its initial size, it also loses the benefits of the mild heating step and means a return to its martensitic phase. Accordingly, it is highly beneficial to obtain a recovered deformation close to 0%, which results in an alloy that is easier to shape by mechanical deformation (stamping, cold rolling%) due to a reduced shape memory.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP21150617.5A EP4026923A1 (de) | 2021-01-07 | 2021-01-07 | Legierung auf der basis von gold und titan |
PCT/EP2022/050214 WO2022148817A1 (en) | 2021-01-07 | 2022-01-06 | Gold and titanium based alloy |
Publications (1)
Publication Number | Publication Date |
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EP4274916A1 true EP4274916A1 (de) | 2023-11-15 |
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ID=74105956
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP21150617.5A Withdrawn EP4026923A1 (de) | 2021-01-07 | 2021-01-07 | Legierung auf der basis von gold und titan |
EP22700363.9A Pending EP4274916A1 (de) | 2021-01-07 | 2022-01-06 | Gold- und titanbasierte legierung |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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EP21150617.5A Withdrawn EP4026923A1 (de) | 2021-01-07 | 2021-01-07 | Legierung auf der basis von gold und titan |
Country Status (2)
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EP (2) | EP4026923A1 (de) |
WO (1) | WO2022148817A1 (de) |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US5853661A (en) * | 1994-07-05 | 1998-12-29 | Cendres Et Metaux Sa | High gold content bio--compatible dental alloy |
ITFI20060206A1 (it) | 2006-08-11 | 2008-02-12 | Consiglio Nazionale Ricerche | Leghe preziose basate sul sistema nitiau, con trasformazioni di fase allo stato solido e metodi per la loro produzione e trasformazione |
SG160266A1 (en) * | 2008-09-08 | 2010-04-29 | Autium Pte Ltd | Coloured gold alloy and method for forming the same |
EP3040790A1 (de) | 2014-12-29 | 2016-07-06 | Montres Breguet S.A. | Uhr oder Schmuckgegenstand aus einer leichten hochwertigen Legierung auf Titanbasis |
FR3063675A1 (fr) | 2017-03-10 | 2018-09-14 | Lvmh Swiss Manufactures Sa | Materiau comprenant une couche mince d'un alliage comportant du titane et de l'or et procede d'obtention d'un tel materiau |
-
2021
- 2021-01-07 EP EP21150617.5A patent/EP4026923A1/de not_active Withdrawn
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2022
- 2022-01-06 WO PCT/EP2022/050214 patent/WO2022148817A1/en unknown
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EP4026923A1 (de) | 2022-07-13 |
WO2022148817A1 (en) | 2022-07-14 |
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