EP2450460A1 - Grey gold alloy with no nickel and no copper - Google Patents
Grey gold alloy with no nickel and no copper Download PDFInfo
- Publication number
- EP2450460A1 EP2450460A1 EP11009183A EP11009183A EP2450460A1 EP 2450460 A1 EP2450460 A1 EP 2450460A1 EP 11009183 A EP11009183 A EP 11009183A EP 11009183 A EP11009183 A EP 11009183A EP 2450460 A1 EP2450460 A1 EP 2450460A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gold alloy
- alloy
- optionally
- element selected
- gray 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.)
- Granted
Links
- 239000003353 gold alloy Substances 0.000 title claims description 21
- 239000010949 copper Substances 0.000 title abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 10
- 229910052802 copper Inorganic materials 0.000 title abstract description 10
- 229910052759 nickel Inorganic materials 0.000 title abstract description 4
- 229910000631 grey gold Inorganic materials 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 40
- 239000000956 alloy Substances 0.000 claims abstract description 40
- 239000010931 gold Substances 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims abstract description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 10
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 7
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000005097 cold rolling Methods 0.000 claims abstract description 3
- 229910001020 Au alloy Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010936 titanium Substances 0.000 abstract description 6
- 239000010938 white gold Substances 0.000 abstract description 6
- 229910000832 white gold Inorganic materials 0.000 abstract description 6
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 abstract description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010791 quenching Methods 0.000 abstract description 2
- 230000000171 quenching effect Effects 0.000 abstract description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 239000010955 niobium Substances 0.000 abstract 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000011701 zinc Substances 0.000 abstract 1
- 238000005266 casting Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002677 Pd–Sn Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 230000002009 allergenic effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 229960004667 ethyl cellulose Drugs 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910002059 quaternary alloy Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention relates to a nickel-free and copper-free gray gold alloy having a hardness particularly suitable for watchmakers, jewelers and jewelers.
- the invention also relates to a process for preparing this alloy.
- gray gold alloys There are two main types of gray gold alloys on the market, nickel alloys and palladium alloys, in which both are used as whiteners.
- Nickel with its allergenic potential tends to be abandoned.
- its alloys exhibit reduced hardness and deformability that lend themselves poorly to the fields of jewelery and watchmaking.
- the increase in the copper concentration is to the detriment of other elements having whitening effects.
- the Japanese patent application published under the number JP-A-8-003662 discloses white gold alloys of the Au-Pd-In, Au-Pd-Sn or Au-Pd-Bi types. These alloys are intended for the preparation of metal clays, that is to say of clays of precious metals.
- Metal clays are indeed generally defined as being a raw material for the manufacture of jewelery or works of art and comprising a very fine powder of precious metals, an organic binder and water. After forming, they are dried and burned to remove the organic binder, so that only the sintered metals remain.
- This Japanese patent application therefore relates to a white gold alloy powder of Au-Pd-In, Au-Pd-Sn or Au-Pd-Bi type to have excellent sinterability. Concretely, by mixing this powder with water, a binder (plasticizer: di-n-butyl phthalate) and a surfactant (ethyl-cellulose), one should obtain a metal clay with a high degree of sintering.
- a gold alloy In order not to require rhodium-plating, a gold alloy must guarantee, according to ASTM Method D1925, a YI value: D1925 ⁇ 19 (YI: "yellowness index”), regarded as "good white” or "premium” and included in the Grade 1 category (see also http://www.utilisegold.com/jewellery technology / colors / whit e guide and Proceedings of Santa Fe Symposium 2005, pp. 103-120 ).
- the colors of the gold alloys are defined in the tri-chromatic space according to the ISO 8654.
- a YI ⁇ 19 value corresponds in first approximation to [-2 ⁇ a ⁇ 2; b ⁇ 10].
- the object of the present invention is to provide a nickel-free and copper-free gray gold alloy having satisfactory mechanical properties as well as a high whiteness (Grade 1) while not requiring rhodium-plating.
- Elements such as Si and Ti are known to those skilled in the art to improve, when added in small amounts, the surface condition and brightness and reduce the risk of corrosion, without substantially modifying the hardness or affect the colour.
- Elements such as Ir, Re or Ru are known to improve the metallurgical properties, in particular to guarantee the fineness of the grain and to avoid the porosities, without appreciably modifying the hardness or affecting the color.
- Table I groups together 18-carat white gold alloys of the state of the art that are commercially available.
- this table gives indications relating to the Vickers HV hardness index of the alloy in the cast state (HV cast), hardened to 75% (HV 75%) and annealed ( HV annealing), as well as to the color measured in the CIELab system.
- alloy No. 6 has a hardly satisfactory HV value, although it contains copper.
- Alloy No. 9 which is composed only of gold and palladium and is therefore free of copper, has a very low annealed HV value.
- Table II below includes gray gold alloys according to the invention which are ternary. TABLE II (invention) Ternary 18-carat gold (% by weight) The at B HV casting HV 75% HV annealing 10 At 75.1 Pd 21.0 In 3.9 78.79 1.49 5.68 80 175 115 11 At 75.1 Pd 22.0 V 2.9 81.04 1.33 5.36 115 195 127 12 At 75.1 Pd 20.0 V 4.9 82.15 1.10 5.03 125 230 157 13 At 75.1 Pd 21.0 Ta 3.9 80.15 1.35 5, 14 135 213 164 14 At 75.1 Pd 23.0 V 1.9 79.34 1.38 5.05 90 182 112 15 At 75.1 Pd 22.0 Sn 2.9 79.54 1.37 5.14 128 202 118 16 At 75.1 Pd 22.0 Zn 2.9 79.36 1.37 4.84 80 156 108 17 At 75.1 Pd 23.5 Zr 1.4 80.06 1.30 4.73 87 179 119 18
- Each of the ternary alloys 10 to 32 according to the invention therefore has satisfactory L, a, b and HV annealing values.
- Table III relates to quaternary and quinternal alloys according to the invention.
- TABLE III (invention) 18 carats quaternary and quinternary (% by weight) The at b HV casting HV 75% HV annealing 33 At 75.1 Pd 21.0 Nb 1.9 Zr 2.0 80.76 1.18 4.53 167 260 169 34 At 75.1 Pd 21.0 Nb 1.9 Mn 2.0 80.41 1.33 4.79 133 213 147 35 At 75.1 Pd 21.0 Zr 2.0 Mn 1.9 79.95 1.24 4.55 150 237 153 36 At 75.1 Pd 19.0 Nb 2.0 Zr 2.0 Mn 1.9 80.77 1.13 4.16 170 285 255 37 At 75.1 Pd 20.0 Zr 2.0 Pt 2.4 Ga 0.5 79.86 1.20 4.65 185 226 192 38 At 75.1 Pd 20.0 Zr 2.5 Pt 2.4 79.96 1.14 4.31 153 209 188
- the grain index is established according to ASTM E 112. TABLE IV (invention) Grain refiner Concentration grain index (Ppm) (ASTM E 112) 39 Iridium 500 2 40 Iridium 1000 3 41 Ruthenium 500 4 42 Ruthenium 1000 7 43 Rhenium 20 5 44 Rhenium 50 6
- the alloys 39 and 40 show a grain structure in columns oriented in the direction of solidification.
- the other alloys exhibit an equiaxed microstructure.
- Ruthenium has the most pronounced grain refining effect, however, there are many inclusions that can penalize polishing.
- Rhenium shows a capacity of refinement of the grain without formation of inclusions. The addition of rhenium at 20 to 60 ppm therefore gives excellent polishing ability.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Adornments (AREA)
Abstract
Description
La présente invention concerne un alliage d'or gris sans nickel et sans cuivre présentant une dureté convenant en particulier aux horlogers, bijoutiers et joailliers. L'invention a également trait à un procédé de préparation de cet alliage.The present invention relates to a nickel-free and copper-free gray gold alloy having a hardness particularly suitable for watchmakers, jewelers and jewelers. The invention also relates to a process for preparing this alloy.
Il existe sur le marché deux principaux types d'alliages d'or gris, les alliages au nickel et les alliages au palladium, dans lesquels ces deux éléments interviennent comme blanchissants.There are two main types of gray gold alloys on the market, nickel alloys and palladium alloys, in which both are used as whiteners.
Le nickel avec son potentiel allergène tend à être abandonné. De plus, ses alliages exhibent une dureté et une déformabilité réduites qui se prêtent mal aux domaines de la bijouterie et de l'horlogerie.Nickel with its allergenic potential tends to be abandoned. In addition, its alloys exhibit reduced hardness and deformability that lend themselves poorly to the fields of jewelery and watchmaking.
De très nombreuses propositions ont donc été avancées pour remplacer le nickel.So many proposals have been made to replace nickel.
Ainsi, les demandes de brevet
L'ajout de cuivre permet de durcir les alliages mais il présente des inconvénients, notamment, une vitesse de refroidissement trop faible (lors de coulées en lingotière), et lors du traitement thermique, un durcissement non contrôlable et un risque de fissuration.The addition of copper makes it possible to harden the alloys but it has drawbacks, in particular, a cooling rate that is too low (during castings in the mold), and during the heat treatment, uncontrollable hardening and a risk of cracking.
De plus, l'augmentation de la concentration en cuivre se fait au détriment d'autres éléments ayant des effets blanchissants.In addition, the increase in the copper concentration is to the detriment of other elements having whitening effects.
En outre, le cuivre comporte un risque d'oxydation.In addition, copper carries a risk of oxidation.
La demande de brevet japonais publiée sous le numéro
Cependant, en ce qui concerne le palladium, ses alliages sans ajout de cuivre sont trop mous compte tenu de la proportion substantielle qu'il faut introduire pour blanchir l'or.However, with regard to palladium, its alloys without the addition of copper are too soft given the substantial proportion that must be introduced to bleach the gold.
Par ailleurs, lors du choix d'un alliage, d'autres paramètres importants sont la couleur et l'éclat du métal. La plupart des alliages contenant du Pd et/ou du Cu requièrent un dépôt galvanique de rhodium afin de se rapprocher de la couleur visée. L'épaisseur de ce revêtement (quelques microns) reste sensible au frottement et la couleur du substrat réapparaît ponctuellement, ce qui ne permet pas de réaliser des objets en or destinés à durer.In addition, when choosing an alloy, other important parameters are the color and brightness of the metal. Most alloys containing Pd and / or Cu require galvanic deposition of rhodium to approximate the target color. The thickness of this coating (a few microns) remains sensitive to friction and the color of the substrate reappears punctually, which does not allow to make gold objects to last.
Afin de ne pas nécessiter de rhodiage, un alliage d'or doit garantir, d'après la norme ASTM Method D1925, une valeur YI : D1925 < 19 (YI : « yellowness index »), considérée comme « good white » ou « premium » et intégrée à la catégorie Grade 1 (voir également
La valeur YI peut être transposée dans le système CIELab, CIE étant le sigle de la Commission Internationale de l'Eclairage et Lab les trois axes de coordonnées, l'axe L mesurant la composante blanc-noir (noir = 0 et blanc = 100), l'axe a mesurant la composante rouge-vert (rouge = valeurs positives, vert = valeurs négatives) et l'axe b mesurant la composante jaune-bleu (jaune = valeurs positives, bleu = valeurs négatives). (Cf. norme ISO 7724 établie par la Commission Internationale de l'Eclairage).The value YI can be transposed into the CIELab system, CIE being the acronym of the International Commission on Illumination and Lab the three coordinate axes, the L axis measuring the white-black component (black = 0 and white = 100) , the axis measuring the red-green component (red = positive values, green = negative values) and the b axis measuring the yellow-blue component (yellow = positive values, blue = negative values). (See ISO 7724 standard issued by the International Commission on Illumination).
Les couleurs des alliages d'or sont définies dans l'espace tri-chromatique selon la norme ISO 8654. Une valeur YI < 19 correspond en première approximation à [-2 ≤ a ≤ 2 ; b ≤ 10].The colors of the gold alloys are defined in the tri-chromatic space according to the ISO 8654. A YI <19 value corresponds in first approximation to [-2 ≤ a ≤ 2; b ≤ 10].
Le but de la présente invention est de proposer un alliage d'or gris sans nickel et sans cuivre présentant des propriétés mécaniques satisfaisantes ainsi qu'une grande blancheur (de Grade 1) tout en ne nécessitant pas de rhodiage.The object of the present invention is to provide a nickel-free and copper-free gray gold alloy having satisfactory mechanical properties as well as a high whiteness (Grade 1) while not requiring rhodium-plating.
Ce but est atteint par un alliage constitué de (en pourcentages massiques) :
- plus de 75% d'Au ;
- de plus de 18% à moins de 24% de Pd ;
- de plus de 1% à moins de 6% d'au moins un élément choisi parmi Mn, Hf, Nb, Pt, Ta, V, Zn et Zr ;
- éventuellement, au plus 0,5% d'au moins un élément choisi parmi Si, Ga et Ti ; et
- éventuellement, au plus 0,2% d'au moins un élément choisi parmi Ru, Ir et Re ;
- la somme de tous ces pourcentages étant bien entendu égale à 100%.
- more than 75% Au;
- from more than 18% to less than 24% of Pd;
- from more than 1% to less than 6% of at least one element selected from Mn, Hf, Nb, Pt, Ta, V, Zn and Zr;
- optionally, at most 0.5% of at least one element selected from Si, Ga and Ti; and
- optionally, at most 0.2% of at least one element selected from Ru, Ir and Re;
- the sum of all these percentages being of course equal to 100%.
En effet, les longues et intenses recherches menées par les inventeurs leur ont permis de découvrir qu'un tel alliage répond à l'ensemble des critères requis pour des alliages destinés à la bijouterie et à l'horlogerie en particulier, aussi bien du point de vue de l'éclat et de la couleur que de celui de la résistance à la corrosion et de la capacité à être travaillé et poli, tout en offrant une dureté comparable ou supérieure aux ors gris contenant du cuivre.Indeed, the long and intense research carried out by the inventors allowed them to discover that such an alloy meets all the criteria required for alloys intended for jewelery and watchmaking in particular, both from the the brilliance and color of corrosion resistance and the ability to be worked and polished, while offering a hardness comparable or superior to gray gold containing copper.
L'alliage d'or gris selon l'invention peut être préparé suivant un procédé dans lequel :
- on place les composants de l'alliage d'or gris dans un creuset ;
- on chauffe le creuset jusqu'à fusion des composants ;
- on coule l'alliage fondu ;
- on le laisse se solidifier ;
- on lui fait subir une trempe à l'eau ;
- on lui fait subir au moins un laminage à froid ; et on le recuit sous atmosphère réductrice.
- the components of the gray gold alloy are placed in a crucible;
- the crucible is heated until the components have melted;
- casting the molten alloy;
- it is allowed to solidify;
- it is tempered with water;
- it is subjected to at least one cold rolling; and annealing under a reducing atmosphere.
La composition générale de l'alliage d'or gris selon l'invention est indiquée ci-dessus.The general composition of the gray gold alloy according to the invention is indicated above.
La composition préférée de l'alliage d'or gris selon l'invention est la suivante (exprimée en pourcentages massiques) :
- plus de 75% d'Au ;
- de 19% à 23,5% de Pd ;
- de 1,4% à 5,9% d'au moins un élément choisi parmi Mn, Hf, Nb, Pt, Ta, V, Zn et Zr ;
- éventuellement, au plus 0,5% d'au moins un élément choisi parmi Si, Ga et Ti ; et
- éventuellement, au plus 0,1% d'au moins un élément choisi parmi Ru, Ir et Re.
- more than 75% Au;
- from 19% to 23.5% of Pd;
- from 1.4% to 5.9% of at least one member selected from Mn, Hf, Nb, Pt, Ta, V, Zn and Zr;
- optionally, at most 0.5% of at least one element selected from Si, Ga and Ti; and
- optionally, at most 0.1% of at least one element selected from Ru, Ir and Re.
D'autres caractéristiques de l'alliage d'or gris selon l'invention, qui sont avantageuses individuellement ou en combinaison, s'énoncent comme suit :
- l'alliage comprend au moins 20% de Pd ;
- il comprend au moins 1,5% de Zr ou de Nb ;
- il comprend de 0,002% à 0,006% (20 à 60 ppm) de Re ;
- il comprend environ 75,1% d'Au.
- the alloy comprises at least 20% Pd;
- it comprises at least 1.5% of Zr or Nb;
- it comprises from 0.002% to 0.006% (20 to 60 ppm) of Re;
- it comprises about 75.1% of Au.
Les éléments tels que Si et Ti sont connus de l'homme du métier pour améliorer, lorsqu'ils sont ajoutés en petites quantités, l'état de surface et l'éclat et diminuer les risques de corrosion, sans modifier sensiblement la dureté ni affecter la couleur.Elements such as Si and Ti are known to those skilled in the art to improve, when added in small amounts, the surface condition and brightness and reduce the risk of corrosion, without substantially modifying the hardness or affect the colour.
Les éléments comme Ir, Re ou Ru sont connus pour améliorer les propriétés métallurgiques, en particulier garantir la finesse du grain et éviter les porosités, sans modifier sensiblement la dureté ni affecter la couleur.Elements such as Ir, Re or Ru are known to improve the metallurgical properties, in particular to guarantee the fineness of the grain and to avoid the porosities, without appreciably modifying the hardness or affecting the color.
Quelle que soit sa formulation, l'alliage selon l'invention répond toujours aux conditions suivantes :
- -2 ≤ a ≤ 2
- b ≤ 10 et
- HV recuit (indice de dureté Vickers après recuit) > 85.
- -2 ≤ a ≤ 2
- b ≤ 10 and
- HV annealed (Vickers hardness value after annealing)> 85.
Ces propriétés sont celles que doit posséder un alliage d'or gris pour satisfaire aux exigences des horlogers, bijoutiers et joailliers.These properties are those that must have a gray gold alloy to meet the requirements of watchmakers, jewelers and jewelers.
Les alliages selon l'invention sont préparés dans les conditions suivante :
- les principaux éléments entrant dans la composition de l'alliage ont de préférence une pureté de 99,95% à l'exception de l'or avec 99,99% et du Zr avec 99,8% ;
- l'alliage est obtenu par fusion des éléments dans un creuset (par exemple en ZrO2). Le chauffage est obtenu par induction dans un four étanche sous pression partielle (par exemple d'argon à 800 mbar). L'alliage en fusion est ensuite coulé dans une lingotière en graphite. Après solidification, la lingotière est sortie du four étanche et le lingot est démoulé, refroidi par une trempe à l'eau et éventuellement écrouté ;
- le lingot est ensuite laminé une ou plusieurs fois à froid, jusqu'à obtention d'un taux d'écrouissage de 75 à 80% ;
- le recuit est réalisé sous atmosphère réductrice (de préférence 80% N2-20% H2) durant 30 minutes à 850°C.
- the main components in the alloy composition preferably have a purity of 99.95% with the exception of gold with 99.99% and Zr with 99.8%;
- the alloy is obtained by melting the elements in a crucible (for example in ZrO 2 ). The heating is obtained by induction in a sealed oven under partial pressure (for example argon at 800 mbar). The molten alloy is then cast in a graphite mold. After solidification, the mold is removed from the sealed oven and the ingot is demolded, cooled by quenching with water and optionally crushed;
- the ingot is then rolled one or more times cold, until a hardening rate of 75 to 80%;
- the annealing is carried out under a reducing atmosphere (preferably 80% N 2 -20% H 2 ) for 30 minutes at 850 ° C.
Dans les exemples qui vont suivre, le Tableau I regroupe des alliages en or gris 18 carats de l'état de la technique que l'on trouve dans le commerce.In the examples that follow, Table I groups together 18-carat white gold alloys of the state of the art that are commercially available.
Outre la composition des alliages donnée en % massiques, ce tableau donne des indications relatives à l'indice de dureté Vickers HV de l'alliage à l'état coulé (HV coulée), écroui à 75% (HV 75%) et recuit (HV recuit), ainsi qu'à la couleur mesurée dans le système CIELab.
(2) : d'après EP1010768
(2): according to EP1010768
On constate que les conditions précitées :
- -2 ≤ a ≤ 2
- b ≤ 10 et
- HV recuit > 85
- -2 ≤ a ≤ 2
- b ≤ 10 and
- HV annealing> 85
De plus, l'alliage n° 6 présente une valeur HV à peine satisfaisante, bien qu'il contienne du cuivre.In addition, alloy No. 6 has a hardly satisfactory HV value, although it contains copper.
L'alliage n°9, qui n'est composé que d'or et de palladium et est donc dépourvu de cuivre, présente une valeur HV recuit très basse.Alloy No. 9, which is composed only of gold and palladium and is therefore free of copper, has a very low annealed HV value.
Le Tableau II suivant regroupe des alliages d'or gris selon l'invention qui sont ternaires.
Chacun des alliages ternaires n° 10 à 32 selon l'invention présente donc des valeurs L, a, b et HV recuit satisfaisantes.Each of the ternary alloys 10 to 32 according to the invention therefore has satisfactory L, a, b and HV annealing values.
Le Tableau III suivant est relatif à des alliages quaternaires et quinternaires selon l'invention.
On constate que les alliages selon l'invention quaternaires n° 33 à 35 et 38 et quinternaires n° 36 et 37 ont tous des valeurs L, a, b et HV recuit satisfaisantes.It is found that Quaternary alloys Nos. 33 to 35 and 38 and Quinternaries Nos. 36 and 37 all have satisfactory L, a, b and HV annealing values.
Dans le tableau IV suivant sont reportés les effets des affineurs de grains couramment employés dans les or gris 18 carats, sur un alliage selon l'invention composé de 75,3 Au, 21,7 Pd et 3,0 Zr (en % en poids).In the following Table IV are reported the effects of grain refiners commonly employed in 18-carat white gold, on an alloy according to the invention composed of 75.3 Au, 21.7 Pd and 3.0 Zr (in% by weight ).
On constate que les valeurs L, a et b d'un tel alliage ne sont pas affectées par l'ajout de l'affineur de grains.It can be seen that the values L, a and b of such an alloy are not affected by the addition of the grain refiner.
L'indice de grains est établi selon la norme ASTM E 112.
De plus, tous les alliages du tableau IV présentent une dureté satisfaisante après recuit.In addition, all the alloys of Table IV have a satisfactory hardness after annealing.
Par ailleurs, les alliages 39 et 40 montrent une structure de grains en colonnes orientées dans le sens de la solidification. Les autres alliages exhibent une microstructure équiaxe. Le ruthénium a l'effet d'affineur de grain le plus prononcé, cependant, on relève de nombreuses inclusions pouvant pénaliser le polissage. Le rhénium montre une capacité d'affinement du grain sans formation d'inclusions. L'ajout de rhénium à hauteur de 20 à 60 ppm confère par conséquent une excellente aptitude au polissage.Moreover, the alloys 39 and 40 show a grain structure in columns oriented in the direction of solidification. The other alloys exhibit an equiaxed microstructure. Ruthenium has the most pronounced grain refining effect, however, there are many inclusions that can penalize polishing. Rhenium shows a capacity of refinement of the grain without formation of inclusions. The addition of rhenium at 20 to 60 ppm therefore gives excellent polishing ability.
Claims (13)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11009183.2A EP2450460B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09405077A EP2251444A1 (en) | 2009-05-06 | 2009-05-06 | Grey gold alloy with no nickel and no copper |
EP10716257.0A EP2427582B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
EP11009183.2A EP2450460B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP10716257.0 Division | 2010-04-15 | ||
EP10716257.0A Division-Into EP2427582B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2450460A1 true EP2450460A1 (en) | 2012-05-09 |
EP2450460B1 EP2450460B1 (en) | 2013-09-25 |
Family
ID=41127638
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09405077A Withdrawn EP2251444A1 (en) | 2009-05-06 | 2009-05-06 | Grey gold alloy with no nickel and no copper |
EP11009183.2A Active EP2450460B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
EP11009184.0A Active EP2450461B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
EP10716257.0A Active EP2427582B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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EP09405077A Withdrawn EP2251444A1 (en) | 2009-05-06 | 2009-05-06 | Grey gold alloy with no nickel and no copper |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP11009184.0A Active EP2450461B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
EP10716257.0A Active EP2427582B1 (en) | 2009-05-06 | 2010-04-15 | Grey gold alloy with no nickel and no copper |
Country Status (6)
Country | Link |
---|---|
US (1) | US9650697B2 (en) |
EP (4) | EP2251444A1 (en) |
JP (1) | JP5793136B2 (en) |
CN (1) | CN102549179B (en) |
CH (1) | CH703415B1 (en) |
WO (1) | WO2010127458A1 (en) |
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CN104884650B (en) * | 2012-11-08 | 2017-09-05 | 贺利氏有限公司 | Nickeliferous billon with low nickel rate of release, the intermediate alloy for obtaining the nickeliferous billon and the wherein purposes of metallic element |
JP2016505710A (en) | 2012-12-03 | 2016-02-25 | アルゴー−ヘラエウス エスエー | Discoloration-resistant gold alloy |
CH707539B1 (en) * | 2013-02-06 | 2017-01-13 | Rolex Sa | Pink gold alloy for timepiece. |
EP3020835B1 (en) | 2014-11-17 | 2021-04-21 | Omega SA | Piece of watchmaking, bijouterie or jewelry comprising a component made of a palladium-based alloy |
EP3070182B1 (en) * | 2015-03-17 | 2017-08-30 | The Swatch Group Research and Development Ltd. | White-gold alloy |
FR3034106B1 (en) | 2015-03-23 | 2022-07-22 | Centre Nat Rech Scient | MONOPHASIC ALLOY OF GOLD AND TUNGSTEN |
EP3315620B1 (en) * | 2016-10-25 | 2020-06-24 | Nivarox-FAR S.A. | Non-magnetic precious alloy for clockmaking applications |
EP3339455B1 (en) * | 2016-12-20 | 2020-02-05 | Montres Breguet S.A. | Grey-gold alloy |
CN110446794B (en) * | 2017-03-27 | 2021-03-26 | 派特·古普塔 | Hard gold alloy containing zirconium, titanium and magnesium for jewelry manufacture |
CH715203B1 (en) | 2018-07-26 | 2022-03-15 | Px Services Sa | Gold-based alloy exhibiting a color change and its use in the field of jewelery and watchmaking. |
CN109136625A (en) * | 2018-09-14 | 2019-01-04 | 深圳市品越珠宝有限公司 | A kind of high hardness alloy and preparation method thereof |
CN110629062A (en) * | 2019-05-16 | 2019-12-31 | 杭州辰卓科技有限公司 | 20K corrosion-resistant brittle fracture-resistant gold alloy with spotty effect and process thereof |
JP6789528B1 (en) * | 2019-09-26 | 2020-11-25 | 田中貴金属工業株式会社 | Medical Au-Pt-Pd alloy |
EP3808865B1 (en) | 2019-10-17 | 2023-01-18 | Richemont International S.A. | White gold alloy and method for manufacturing same |
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Also Published As
Publication number | Publication date |
---|---|
CH703415B1 (en) | 2014-03-14 |
JP2012526192A (en) | 2012-10-25 |
EP2450460B1 (en) | 2013-09-25 |
CN102549179B (en) | 2016-03-30 |
WO2010127458A8 (en) | 2011-04-14 |
EP2427582A1 (en) | 2012-03-14 |
EP2427582B1 (en) | 2014-03-12 |
JP5793136B2 (en) | 2015-10-14 |
EP2450461A1 (en) | 2012-05-09 |
EP2450461B1 (en) | 2014-10-29 |
EP2251444A1 (en) | 2010-11-17 |
WO2010127458A1 (en) | 2010-11-11 |
CN102549179A (en) | 2012-07-04 |
US9650697B2 (en) | 2017-05-16 |
US20120114522A1 (en) | 2012-05-10 |
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