Classifications

• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B19/00—Indicating the time by visual means
  • G04B19/06—Dials
  • G04B19/12—Selection of materials for dials or graduations markings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21B—ROLLING OF METAL
  • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
  • B21B1/16—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling wire rods, bars, merchant bars, rounds wire or material of like small cross-section
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
  • B21B—ROLLING OF METAL
  • B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C30/00—Alloys containing less than 50% by weight of each constituent
  • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C30/00—Alloys containing less than 50% by weight of each constituent
  • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C5/00—Alloys based on noble metals
  • C22C5/02—Alloys based on gold
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C5/00—Alloys based on noble metals
  • C22C5/04—Alloys based on a platinum group metal
• • 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
  • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
• • 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
  • 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
• • G—PHYSICS
  • G04—HOROLOGY
  • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
  • G04B19/00—Indicating the time by visual means
  • G04B19/04—Hands; Discs with a single mark or the like
  • G04B19/042—Construction and manufacture of the hands; arrangements for increasing reading accuracy
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C9/00—Alloys based on copper

Definitions

• the present invention relates to a process for producing an 8 to 11 carat gold alloy wire cast to an initial diameter of less than or equal to 20 mm to obtain a wire of a final diameter which is between the diameter initial cast and 0.1 mm.
• the invention relates to the field of alloy metallurgy for watchmaking and jewelery.
• gray gold alloys There are mainly two types of gray gold alloys on the market: alloys in which the bleaching metal of gold is nickel, and those in which this metal is palladium.
• nickel alloys can still be used in watchmaking for parts that are never in contact with the skin.
• the low material cost of nickel compared to palladium makes them interesting alloys for these horological applications.
• these alloys of nickel gold have a very low chromaticity, which makes them very attractive for their relative whiteness, they can have only one mode of shaping, lost wax casting, because in the annealed state they have a high hardness, typically greater than 260 Hv for an 18K gold alloy with 21% by weight of nickel.
• this hardness makes them little cold deformable and therefore not suitable for the working conditions of jewelers and manufacturers of watchmaking pieces, such as watch cases for hands, dial appliques, etc., the main users of these alloys. .
• alloys with a relatively low gold content typically 9-carat alloys
• Palladium gold alloys are expensive given the price of palladium, and because it must be added to the alloy in substantial amounts to achieve a whitening effect. Furthermore the hardness of palladium gold alloys typically 120 HV certainly allows satisfactory cold deformation but is however not sufficient to meet the requirements for the realization of watchmaking parts.
• cobalt which has properties close to those of nickel, may be substituted at least partially for nickel, but this substitution greatly increases most of the mechanical characteristics to the detriment of the ductility of the alloy.
• the low-grade silver does not participate in a whitening effect, but since it is relatively neutral in the metallurgical properties of gold alloys, it can be used to make the balance to complete the composition of the title, with the disadvantage of bringing beyond a few percent the tarnishing of the alloy, and also to promote a demixtion with the ferrous elements: nickel, cobalt and iron, thus causing the ferromagnetic effect.
• the market has already attempted to remedy the aforementioned problems by proposing a nickel-white or gray-nickel alloy comprising, expressed by mass, between 37.5 and 37.7% of gold, of the order of 9% nickel, of the order of 2% of palladium, of the order of 9% silver, of the order of 32% of Cu and of the order of 10% of zinc, the rest being formed of different elements intended for improve the properties of the alloy.
• This gray gold alloy has a good resistance to cracking under various conditions of mechanical stress, including fatigue and cold deformation, but its relative low nickel content makes it on the other hand a color with yellow reflections that does not allow him to meet the whiteness criteria required for use in jewelery or watchmaking.
• This alloy of white or gray nickel gold comprises, expressed by mass, between 37.5 and 37.7% of gold, of the order of 19% of nickel, of the order of 31% of Cu, of about 12% of zinc and about 0.5% of manganese, the rest being formed of different elements to improve the properties of the alloy.
• This gray gold alloy has a luster and a color meeting the criteria required for use in jewelery or watchmaking, but it however has a poor resistance to cracking under various stress conditions, especially during recrystallization heat treatments .
• the present invention therefore aims to determine the conditions for obtaining gold alloy wire to substantially improve white or gray gold alloys by providing a gray gold alloy without cobalt, without iron, without silver palladium-free and high-nickel content to remove palladium without reducing its deformability properties and metallurgical properties, and by the obtaining of small diameter wire of good metallurgical quality, homogeneous and without micro-cracks.
• the invention relates to a process for producing an 8-11 carat gold alloy wire cast to an initial diameter of less than or equal to 20 mm to obtain a wire of a final diameter between initial diameter cast and 0.1 mm, according to claim 1.
• the development of the invention allows the selection of a cobalt-free, iron-free, silver-free and palladium-free, high-nickel nickel-free gold alloy whose deformability allows it to be processed by the drawing technique. cold without risk of cracking, and which is economical to achieve and easy to implement.
• An advantage of the present invention is the obtaining of a gold alloy wire having an interesting compromise between a color and a brightness of a whiteness sufficient to meet the aesthetic requirements of the field of watchmaking and the resistance to cracking during its forming by cold deformation.
• Another advantage is the ease of polishing, and obtaining a great whiteness after polishing.
• the deformation of the section is limited to a value of less than or equal to 13% per pass.
• the number of anneals is limited to three.
• the number of stretching passes is limited to three.
• the wire obtained by these stretching passes is straightened.
• the profiled wire is cut to length after its complete elaboration.
• At least one of the elements Ir, Ti, Si is incorporated in the alloy composition between 0.002% and 1,000% by weight percentage of the total.
• Si is incorporated between 0.30% and 1.00% by weight percent of the total.
• Ti is incorporated between 20 and 500 ppm.
• Re is included between 0.000% and 0.002% by weight percent of the total.
• In is incorporated between 1.00% and 4.00% by weight percent of the total.
• said wire is made with a diameter greater than or equal to 0.1 mm.
• said wire is made with a diameter less than or equal to 20.0 mm.
• this wire is converted by stamping to form a dial, or a dial applique, or a needle.
• the gold alloy is a 7-carat alloy and comprises, expressed by mass, between 29 and 30% of gold, between 4.8 and 13% of Zn, between 24.2 and 47% of Cu and between 13 and 35% of nickel, and possibly at most 5% of at least one of the elements selected from Ir, In, Ti, Si, Ga, Re.
• the gold alloy is a 9-carat alloy and comprises between 37.5 and 38.5% of gold, between 4.2 and 11.5% of Zn, between 21.5 and 41.5% Cu and between 11.5 and 31.2% nickel, and optionally at most 5% of at least one of the elements selected from Ir, In, Ti, Si, Ga, Re.
• the gold alloy is a 10 carat alloy and comprises, expressed by mass, between 41.5 and 42.5% of gold, between 3.9 and 10, 7% of Zn, between 19.9 and 38.8% of Cu and between 10.7 and 29.1% of nickel, and possibly at most 5% of at least one of the elements selected from Ir, In, Ti, If, Ga, Re.
• the gold alloy is a 13-carat alloy and has, expressed by mass, between 54 and 55% Au, between 3.1 and 8.4% of Zn, between 15.7 and 30.4% Cu and between 8.4 and 22.8% nickel, and optionally at most 5% of at least one of the elements selected from Ir, In, Ti, Si, Ga, Re .
• the gold alloy comprises at least one of the elements Ir, Ti, Si, in a proportion for each element of between 0.002 and 1% by weight, and, when it comprises If, the proportion of Si is preferably 0.3 to 1% by weight, and when it comprises Ti, the proportion of Ti is preferably 20 to 500 ppm, and when it comprises Re, the proportion Re is preferably 0.002% by weight, and when it comprises indium, the proportion of indium is preferably between 1 and 4% by weight.
• the gold alloys according to the invention find particular application for the production of timepieces, jewelery or jewelery and in particular for the production of dials, dial appliques and indicator needles for coin watchmaking.
• this alloy makes it possible in particular to avoid the galvanic deposition of rhodium which is commonly used in the horological field to give the treated parts a brightness and a color of satisfactory whiteness.
• the elements of the composition of the alloy are placed in a crucible which is heated until the elements are melted.
• the heating is carried out in a sealed induction furnace under partial pressure of nitrogen.
• the molten alloy is cast in an ingot mold.
• the ingot After solidification, the ingot is subjected to quenching with water.
• the hardened ingot is then cold rolled and annealed.
• the degree of hardening between each annealing is 66 to 80%, and preferably between 60 and 75%.
• Each anneal lasts 20 to 30 minutes and is between 600 and 650 ° C under a reducing atmosphere composed of N 2 and H 2 .
• Cooling after annealing can be done by quenching with water.
• Alloy No. 0 is an alloy of the prior art which is not white enough for lack of nickel and No. 1 and 2 alloys made and tested by the plaintiff crack during thermal recrystallization treatments.
• compositions of the invention namely alloys Nos. 3 to 8 have been developed and tested in deformation to meet the triple stress of brightness, whiteness and deformation capacity required for alloys intended to be used in watchmaking and jewelery and have responded satisfactorily.
• Table 2 gives in particular the indications relating to the hardness of the alloy in the cast, annealed and hardened state. as well as the color measured in a three-axis coordinate system.
• alloy No. 0 of the prior art has a strong component b * which gives it an unacceptable yellowish appearance for a watchmaking application while the alloys of the invention No. 3 to No. 5 have a component b * significantly lower making the yellowish component of the color of the alloy imperceptible to the naked eye.
• Alloys No. 1 and 2 meet the aesthetic criteria in terms of color but are not allowed to deform mechanically cold without cracking.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Crystallography & Structural Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Manufacturing & Machinery (AREA)
• Adornments (AREA)
• Metal Rolling (AREA)
• Conductive Materials (AREA)

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• 2015
  • 2015-11-05 EP EP15193182.1A patent/EP3165621A1/fr not_active Withdrawn
• 2016
  • 2016-09-21 EP EP16189866.3A patent/EP3165622B1/fr active Active
  • 2016-10-24 JP JP2016207636A patent/JP6263245B2/ja active Active
  • 2016-11-03 US US15/342,270 patent/US10471486B2/en active Active
  • 2016-11-03 RU RU2016143464A patent/RU2720374C2/ru active
  • 2016-11-04 CN CN201610962907.5A patent/CN106676368B/zh active Active

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