EP3121297A1 - Herstellungsverfahren einer schmuckkomponente aus platinlegierung - Google Patents

Herstellungsverfahren einer schmuckkomponente aus platinlegierung Download PDF

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Publication number
EP3121297A1
EP3121297A1 EP16177653.9A EP16177653A EP3121297A1 EP 3121297 A1 EP3121297 A1 EP 3121297A1 EP 16177653 A EP16177653 A EP 16177653A EP 3121297 A1 EP3121297 A1 EP 3121297A1
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EP
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Prior art keywords
hardness
semi
finished product
alloy
process according
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Granted
Application number
EP16177653.9A
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English (en)
French (fr)
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EP3121297B1 (de
Inventor
Fréderic Diologent
Damien Colas
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Richemont International SA
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Cartier International AG
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    • 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
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal

Definitions

  • the present invention relates to a method for obtaining a platinum alloy ornament component containing at least 80% by weight of platinum, having a particularly high hardness and can be machined by the usual methods.
  • the component is intended for applications in watchmaking, jewelery, jewelery, eyewear, writing instruments, luxury accessories, and other decorative or functional applications in which the visual aspect is also important.
  • the document EP0621349 describes a process for curing platinum at the surface by a surface layer containing boron.
  • the process described only allows the treatment of a finished part, and tends to affect the aesthetic aspect of the latter (hue and temperature).
  • the surface can be damaged. Refurbishment or refurbishment of such a room requires a specific post-restoration process that can be conducted only under very specific conditions and is therefore not within the reach of restoration workshops equipped with conventional means.
  • the document GB2279967 proposes a high purity platinum alloy containing cerium in a small amount.
  • This alloy makes it possible to achieve hardness comparable to, or even slightly greater than, that of a standard platinum alloy.
  • cerium is a very sensitive element to oxidation, the preparation of the alloy must be carried out under vacuum or under an inert gas, making the process complex.
  • cerium has a medium solid solubility in platinum, which also limits the homogeneity of the alloy obtained.
  • the document GB578956 proposes a platinum alloy cured by the addition of oxides by means of a sintering process.
  • the process is complex and is dependent on the size of the powders and the homogeneity of the compound to be obtained.
  • the document JP1988145759 proposes a platinum alloy containing in particular iron, palladium and copper, and the hardening is obtained in part by a plastic deformation operation to the shape of the part to be obtained and by a heat treatment operation after the steps of setting in shape.
  • This solution is therefore limited on the one hand by expensive matrix tools, and on the other hand by the heat treatment step which could promote recrystallization of the material, or even cause surface texture to appear.
  • the document EP0947595 discloses a platinum alloy cured by dispersion reinforcement. This alloy uses dispersion oxides to oxidize the non-noble metal. On the other hand, the dispersing elements tend not only to disadvantage the wear of the tools, but they also make difficult the polishing steps.
  • Heat treatment hardening processes on finished platinum alloy components are, on the other hand, known. They have the disadvantage that the grain structure is modified, which affects the texture of the polished surfaces.
  • EP2705170A1 proposes a process for obtaining a platinum alloy with very high hardness through an amorphous structure, namely a metal glass.
  • This high hardness involves a material and a method of shaping very particular and also require very specific tools and associated costs very high.
  • the application of this technology to a wide range of products, highly diversified in their geometries, is therefore not the most suitable from an industrial point of view.
  • the component obtained by the process of the invention has a hardness typically 25% to 50% higher than the hardness of the starting alloy.
  • the method makes it possible to obtain the component in its final form and hardness without the need for heat treatment on the final component to modify its hardness.
  • the purpose of the severe plastic deformation cycle (s) of the hardening step is to transform the crystallographic structure of the platinum alloy into an ultrafine grained ( UFG) structure.
  • ultrafine grain structure we mean a structure whose grain size is at least less than 1 ⁇ m in at least one grain orientation.
  • the grain size of the ultrafine grain structure may be less than 500 nm, and even less than 200 nm, see 100 nm.
  • the deformation (or the relative elongation, noted ⁇ ) can be up to 5, or more.
  • the alloy comprises at least 80.0% platinum and one or more of the following chemical elements: between 0% and 4% indium; between 0% and 6% ruthenium; between 0% and 5% copper; between 0% and 5% cobalt; between 0% and 20% of iridium; between 0% and 10% nickel; between 0% and 20% hafnium; between 0% and 20% tin; between 0% and 20% tungsten; between 0% and 15% of palladium; between 0% and 3% gallium; between 0% and 20% rhodium; between 0% and 20% scandium; between 0% and 8% of tungsten; and between 0% and 5% gold.
  • the severe plastic deformation cycle (s) can be realized using one of the methods, or a combination of these methods, including: equal channel angular pressing (ECAP ), angular extrusion according to equal channels (ECAP- accordance), high pressure torsion (high pressure torsion tube twisting orhigh pressure, HPT or HPTT), accumulative roll-bonding (accumulative roll bonding, ARB), repetitive corrugation and straightening (straightening and repetitive corrugation, RCS) , asymmetric rolling (asymmetric rolling, ASR), cyclic extrusion-compression (cyclic extrusion compression CEC), roll drawing (rotary swaging), or any other suitable method for obtaining said ultrafine-grained structure.
  • ECAP equal channel angular pressing
  • ECAP- accordance high pressure torsion
  • HPT or HPTT high pressure torsion tube twisting orhigh pressure, HPT or HPTT
  • accumulative roll-bonding accumulative roll bonding
  • ARB repetitive corrugation and straightening
  • RCS
  • the method comprises a step of shaping the alloy so as to give the semi-finished product a particular shape.
  • the semi-finished product may take the form of a plate, a bar, an ingot, a billet, or any other advantageous form for the subsequent machining step.
  • the method also comprises a step comprising one or more heat recovery treatments.
  • Restoration heat treatment can be performed after the severe plastic deformation cycle, or between severe plastic deformation cycles.
  • the parameters of the recovery heat treatment are adjusted so as not to completely relax the platinum alloy, so as not to degrade the second hardness obtained during the work hardening step.
  • the (or) heat recovery treatment is performed at a temperature below 600 ° C beyond which the mechanical properties of the alloy drop rapidly and the ductility increases.
  • the heat treatment (s) is preferably carried out at a temperature above 250 ° C and below 600 ° C. Indeed, below 250 ° C, the restoration heat treatment may have little or no effect for treatment times that are less than 1 hour, the thermal activation is not sufficient.
  • the figure 1 reports the evolution of the elastic limit (Rm in MPa) and the maximum stress (Rp0.2 in MPa) for an alloy comprising at least 80.0% platinum as a function of temperature.
  • the figure 2 reports the evolution of the hardness (HV) of the same alloy as a function of temperature.
  • the (or) heat treatment of restoration is preferably carried out at a temperature between 250 ° C and 500 ° C, or even between 250 ° C and 400 ° C.
  • the recovery heat treatment time may be one hour or less than one hour.
  • the process comprises one or more heat treatment cures.
  • the heat treatment or treatments for hardening further increase the second hardness of the semi-finished product by the precipitation of the alloying elements.
  • the process of the invention provides the semi-finished product with a second hardness which is at least 25% and even 50% higher than the first hardness of the starting alloy.
  • the machining step may include a material removal process such as turning, milling, grinding, spark erosion, cutting, laser or water jet cutting, or any other suitable method.
  • the machining step may also include a method of shaping by deformation or assembly.
  • the machining step can also include one or more finishing treatments, such as machining, satin finishing, polishing, sanding, microbilling, etching or any other suitable mechanical process.
  • the machining step makes it possible to obtain the component in its final shape and hardness. It is therefore not necessary to perform heat treatment on the component obtained by the present process to modify its hardness. Indeed, the second hardness obtained for the semi-finished product by the hardening step corresponds to the desired hardness of the component.
  • the ornamentation component may comprise a watch component, for example a component of the movement, the bracelet or a dressing component such as the case, the bezel, the bottom.
  • the ornamentation component may also include a component for jewelery, eyewear, writing instruments, luxury accessories (key chains, lighters, cufflinks, tie bars, etc.) and others. decorative or functional applications in which the visual aspect is also important.
  • an alloy comprising about 95% platinum and about 5% ruthenium, having a first nominal hardness of about 120Hv.
  • the alloy is subjected to the first shaping step and the work hardening step having at least one severe plastic deformation cycle, so as to increase the second hardness of the semi-finished product to a value of at least 250 Hv.
  • the cured semi-finished product has a second hardness of about 250 Hv.
  • the hardening step is performed by the high-pressure torsion method, the semi-finished product has a second hardness greater than 400 Hv.
  • an alloy comprising approximately 95% of platinum, between 1% and 4% of copper and between 1% and 4% of gallium (for a total of approximately 5% of copper and gallium) is provided.
  • first nominal hardness of at least 200Hv.
  • the semi-finished product when the work hardening step is performed by the accumulative bonding method, the semi-finished product has a second hardness of about 300 Hv.
  • the semi-finished product can then be subjected to a subsequent curing heat treatment step to increase the second hardness to about 400 Hv.
  • the hardening step comprising at least one severe plastic deformation cycle which may be followed by at least one heat recovery treatment, as described above.
  • the process for obtaining an ornamental component described herein applies to any alloy comprising at least 80% by weight platinum, and may contain one or more of the following chemical elements: between 0% and 4% indium; between 0% and 6% ruthenium; between 0% and 5% copper; between 0% and 5% cobalt; between 0% and 20% of iridium; between 0% and 10% nickel; between 0% and 20% hafnium; between 0% and 20% tin; between 0% and 20% tungsten; between 0% and 15% of palladium; between 0% and 3% gallium; between 0% and 20% rhodium; between 0% and 20% scandium; between 0% and 8% of tungsten; and between 0% and 5% gold.

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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)
EP16177653.9A 2015-07-23 2016-07-01 Herstellungsverfahren einer schmuckkomponente aus platinlegierung Active EP3121297B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH10732015 2015-07-23

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EP3121297A1 true EP3121297A1 (de) 2017-01-25
EP3121297B1 EP3121297B1 (de) 2020-12-16

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107058788A (zh) * 2017-04-12 2017-08-18 深圳市星光达珠宝首饰实业有限公司 一种多元铂钌合金及其制备方法
CN107671159A (zh) * 2017-10-18 2018-02-09 大连理工大学 超声振动辅助脱模的限制性模压模具及晶粒细化方法
CN107893201A (zh) * 2017-11-17 2018-04-10 合肥工业大学 制备超细晶材料的往复挤扭镦等径角成形方法
WO2022074363A1 (en) * 2020-10-05 2022-04-14 Alloyed Limited A platinum alloy composition

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB578956A (en) 1942-02-07 1946-07-18 Lodge Plugs Ltd Improvements relating to sparking plug electrodes
US4165983A (en) * 1977-02-23 1979-08-28 Johnson, Matthey & Co., Limited Jewelry alloys
JPS63145759A (ja) 1986-12-09 1988-06-17 Citizen Watch Co Ltd 装飾用白金合金の熱処理方法
EP0621349A1 (de) 1993-04-23 1994-10-26 Degussa Aktiengesellschaft Oberflächengehärtete Gegenstände aus Platin- und Palladiumlegierungen und Verfahren zu deren Herstellung
GB2279967A (en) 1993-07-14 1995-01-18 Nagahori Kk Platinum alloy
US5846352A (en) * 1996-11-22 1998-12-08 Kretchmer; Steven Heat treatment of a platinum-gallium alloy for jewelry
EP0947595A2 (de) 1998-03-28 1999-10-06 W.C. Heraeus GmbH & Co. KG Verfahren zur Herstellung eines aus dispersionsverfestigtem Platinwerkstoff bestehenden, geschweissten Formkörpers, insbesondere eines Rohres
US6562158B1 (en) * 1998-12-01 2003-05-13 Steven Kretchmer Heat-treatable platinum-gallium-palladium alloy for jewelry
WO2006024928A1 (en) * 2004-09-02 2006-03-09 University Of Cape Town Hardening of metal alloys
WO2012150558A1 (en) * 2011-05-02 2012-11-08 École Polytechnique Fédérale De Lausanne (Epfl) Platinum based alloys

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB578956A (en) 1942-02-07 1946-07-18 Lodge Plugs Ltd Improvements relating to sparking plug electrodes
US4165983A (en) * 1977-02-23 1979-08-28 Johnson, Matthey & Co., Limited Jewelry alloys
JPS63145759A (ja) 1986-12-09 1988-06-17 Citizen Watch Co Ltd 装飾用白金合金の熱処理方法
EP0621349A1 (de) 1993-04-23 1994-10-26 Degussa Aktiengesellschaft Oberflächengehärtete Gegenstände aus Platin- und Palladiumlegierungen und Verfahren zu deren Herstellung
GB2279967A (en) 1993-07-14 1995-01-18 Nagahori Kk Platinum alloy
US5846352A (en) * 1996-11-22 1998-12-08 Kretchmer; Steven Heat treatment of a platinum-gallium alloy for jewelry
EP0947595A2 (de) 1998-03-28 1999-10-06 W.C. Heraeus GmbH & Co. KG Verfahren zur Herstellung eines aus dispersionsverfestigtem Platinwerkstoff bestehenden, geschweissten Formkörpers, insbesondere eines Rohres
US6562158B1 (en) * 1998-12-01 2003-05-13 Steven Kretchmer Heat-treatable platinum-gallium-palladium alloy for jewelry
WO2006024928A1 (en) * 2004-09-02 2006-03-09 University Of Cape Town Hardening of metal alloys
WO2012150558A1 (en) * 2011-05-02 2012-11-08 École Polytechnique Fédérale De Lausanne (Epfl) Platinum based alloys
EP2705170A1 (de) 2011-05-02 2014-03-12 Ecole Polytechnique Fédérale de Lausanne (EPFL) Legierungen auf platinbasis

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BIGGS T ET AL: "THE HARDENING OF PLATINUM ALLOYS FOR POTENTIAL JEWELLERY APPLICATION", PLATINIUM METALS REVIEW, JOHNSON MATTHEY PLC, LONDON, GB, vol. 49, no. 1, 1 January 2005 (2005-01-01), pages 2 - 15, XP009055328, ISSN: 0032-1400, DOI: 10.1595/147106705X24409 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107058788A (zh) * 2017-04-12 2017-08-18 深圳市星光达珠宝首饰实业有限公司 一种多元铂钌合金及其制备方法
CN107671159A (zh) * 2017-10-18 2018-02-09 大连理工大学 超声振动辅助脱模的限制性模压模具及晶粒细化方法
CN107671159B (zh) * 2017-10-18 2020-02-18 大连理工大学 超声振动辅助脱模的限制性模压模具及晶粒细化方法
CN107893201A (zh) * 2017-11-17 2018-04-10 合肥工业大学 制备超细晶材料的往复挤扭镦等径角成形方法
WO2022074363A1 (en) * 2020-10-05 2022-04-14 Alloyed Limited A platinum alloy composition
GB2599462B (en) * 2020-10-05 2023-06-14 Anglo Platinum Marketing Ltd A platinum alloy composition

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