EP3519900A1 - Timepiece component comprising a high-entropy alloy - Google Patents
Timepiece component comprising a high-entropy alloyInfo
- Publication number
- EP3519900A1 EP3519900A1 EP17745346.1A EP17745346A EP3519900A1 EP 3519900 A1 EP3519900 A1 EP 3519900A1 EP 17745346 A EP17745346 A EP 17745346A EP 3519900 A1 EP3519900 A1 EP 3519900A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- entropy alloy
- high entropy
- atomic
- following formula
- component according
- 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
- 239000000956 alloy Substances 0.000 title claims abstract description 56
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 56
- 239000006104 solid solution Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000005097 cold rolling Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 210000003423 ankle Anatomy 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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
- G04B1/00—Driving mechanisms
- G04B1/10—Driving mechanisms with mainspring
- G04B1/14—Mainsprings; Bridles therefor
-
- 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
- G04B1/00—Driving mechanisms
- G04B1/10—Driving mechanisms with mainspring
- G04B1/14—Mainsprings; Bridles therefor
- G04B1/145—Composition and manufacture of the springs
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/30—Ferrous alloys, e.g. steel alloys containing chromium with cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
-
- 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
- G04B13/00—Gearwork
- G04B13/02—Wheels; Pinions; Spindles; Pivots
-
- 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
- G04B29/00—Frameworks
- G04B29/02—Plates; Bridges; Cocks
- G04B29/027—Materials and manufacturing
-
- 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
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
-
- 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
- G04B5/00—Automatic winding up
- G04B5/02—Automatic winding up by self-winding caused by the movement of the watch
- G04B5/16—Construction of the weights
Definitions
- the present invention relates to a clock component comprising a high entropy alloy, and a method of manufacturing such a clock component.
- the invention also relates to the use of a high entropy alloy for manufacturing a watch component.
- the watch components and particularly the barrel springs, are subject to strong constraints, in particular during their manufacturing processes, but also during their use. In particular, they must have high mechanical strength and high ductility.
- watch components rarely simultaneously exhibit these antagonistic characteristics.
- the invention aims to overcome the drawbacks of the state of the art by providing a watch component having a higher mechanical strength and greater ductility.
- a timepiece component comprising a high entropy alloy, the high entropy alloy comprising between 4 and 13 main elements forming a single solid solution, the high entropy alloy having a concentration in each main element between 1 and 55 atomic%.
- a timepiece component comprising a high entropy alloy, the high entropy alloy comprising between 4 and 13 main elements forming a single solid solution, the high entropy alloy having a concentration in each main element between 1 and 55 atomic%.
- the concentration in each main element is between 10 and 55 atomic%. According to various preferred embodiments:
- the high entropy alloy can satisfy the following formula:
- FeaMnbCocCrd wherein a, b, c and d are from 1 to 55 atomic%;
- the high entropy alloy can have the following formula:
- the high-entropy alloy may have the following formula: Fes-x Mn x Co-10 Co, where x is between 25 and 79 at%, and preferably x is between 25 and 45 at%;
- the high entropy alloy can satisfy the following formula:
- FeaMnbNieCocCrd where a, b, c, d and e are between 1 and
- the high entropy alloy can satisfy the following formula Fe2oMn2oNi2oCo2oCr2o;
- the high entropy alloy can satisfy the following formula
- the high entropy alloy can satisfy the following formula:
- the high entropy alloy can in particular correspond to the following formula Ta2oNb2oHf2oZr2oTi2o ;
- the high entropy alloy can satisfy the following formula:
- AlaLibMgcScdTie wherein a, b, c, d and e are from 1 to 55 atomic%; the high entropy alloy may in particular correspond to the following formula Al2oLi2oMgioSc2oTi30;
- the high entropy alloy can satisfy the following formula:
- AlaCobCr c CudFe Nif e wherein a, b, c, d, e and f are from 1 to 55 atomic%.
- the high entropy alloy can satisfy the following formula
- the high entropy alloy may comprise one or more interstitial elements among the following: C, N, B. These interstitial elements make it possible to further increase the mechanical strength of the alloy.
- the high entropy alloy may comprise one or more elements of structural hardening among the following: Ti, Al, Be, Nb, preferably in a mass concentration of between 0.1 and 3%.
- the watch component may be one of the following: a spring, a mainspring, a jumper spring, an anchor, a plate, an anchor, a rod, an anchor rod, an anchor fork , a wheel, an escape wheel, a shaft, a pinion, an oscillating weight, a winding stem, a crown, a watch case, a bracelet link, a watch bezel, a bracelet clasp.
- a second aspect of the invention also relates to the use of a high entropy alloy for manufacturing a watch component, the high entropy alloy comprising between 4 and 13 main elements forming a single solid solution, the alloy having a concentration in each main element between 1 and 55 atomic%.
- FIG. 1 shows schematically a mainspring according to one embodiment of the invention
- FIG. 2 shows schematically the steps of a method of manufacturing a mainspring according to one embodiment of the invention.
- Figure 1 shows a barrel spring 1 according to one embodiment.
- This barrel spring 1 is made of a high entropy alloy.
- the entropy of mixing is high and makes the single phase thermodynamically more stable than the mixing of several phases.
- the barrel spring is preferably made of the high entropy alloy described in the publication "Metastable high-entropy dual-phase alloys overcome the strength-ductility trade-off", Zhiming Li et al, Nature 534, 227-230 (09 June 2016)
- This high entropy alloy has the following formula: Feso-xMnxCo-ioCno.x is preferably 25 to 79 atomic%.
- the mainspring can be achieved in a Fe35Mn 4 5CoioCno alloy.
- the barrel spring thus produced has the advantage of combining a high limit at break and a high ductility.
- the mainspring can be made of a Fe 4 oMn 4 OocoCno alloy.
- the spring thus produced presents the advantage of having a high breaking strength and high ductility. It also operates according to a TWIN mechanism ("twinning induced plasticity").
- the mainspring can be made of Fe 4 Mn 3 O 5 CoO 2 O 2 alloy.
- the barrel spring thus produced has the advantage of still having greater breaking strength and greater ductility. It also works according to a TRIP mechanism ("transformation induced plasticity").
- the barrel spring can be made of a FesoMnsoCo-ioCr-10 alloy.
- the thus-produced barrel spring has the advantage of still having greater breaking strength and greater ductility. It operates according to a TRIP mechanism with the appearance of two phases, cfc and hc, by a clipping mechanism.
- the invention is not limited to the manufacture of a mainspring. Indeed, other watch components could be made in the high entropy alloy Feso-xMnxCo-ioCno, such as a spring, a rod, an ankle, a pendulum, an axis, a plate, an anchor, an anchor rod , an anchor fork, an escape wheel, a shaft, a pinion, an oscillating weight, a winding stem, a crown, a jumping spring, a watch case, a bracelet link, a watch bezel, a bracelet clasp ...
- a spring a rod, an ankle, a pendulum, an axis, a plate, an anchor, an anchor rod , an anchor fork, an escape wheel, a shaft, a pinion, an oscillating weight, a winding stem, a crown, a jumping spring, a watch case, a bracelet link, a watch bezel, a bracelet clasp ...
- FIG. 2 diagrammatically represents the steps of a method of manufacturing the mainspring of FIG. 1.
- This method comprises a first step 101 for manufacturing a high entropy alloy ingot. To do this, the elements are mixed in pure form or pre-alloy, then they are fused and the whole is cast to form an ingot.
- the method then comprises a step 102 of hot forging of the ingot.
- the method then comprises a step 103 of hot rolling.
- the process then comprises a cold rolling step 104.
- the method then comprises a drawing step 105.
- the process then comprises a cold rolling step 106.
- the alloy Feso-xMnxCo-ioCno was used.
- other high entropy alloys could be used, such as:
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Adornments (AREA)
- Heat Treatment Of Articles (AREA)
- Springs (AREA)
- Heat Treatment Of Steel (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16191867.7A EP3301520A1 (en) | 2016-09-30 | 2016-09-30 | Timepiece component having a high-entropy alloy |
PCT/EP2017/069219 WO2018059795A1 (en) | 2016-09-30 | 2017-07-28 | Timepiece component comprising a high-entropy alloy |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3519900A1 true EP3519900A1 (en) | 2019-08-07 |
EP3519900B1 EP3519900B1 (en) | 2021-05-05 |
Family
ID=57103844
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16191867.7A Withdrawn EP3301520A1 (en) | 2016-09-30 | 2016-09-30 | Timepiece component having a high-entropy alloy |
EP17745346.1A Active EP3519900B1 (en) | 2016-09-30 | 2017-07-28 | Timepiece component having a high-entropy alloy |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16191867.7A Withdrawn EP3301520A1 (en) | 2016-09-30 | 2016-09-30 | Timepiece component having a high-entropy alloy |
Country Status (6)
Country | Link |
---|---|
US (3) | US20190235441A1 (en) |
EP (2) | EP3301520A1 (en) |
JP (1) | JP6892914B2 (en) |
CN (1) | CN109804321B (en) |
RU (1) | RU2715832C1 (en) |
WO (1) | WO2018059795A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH714235A1 (en) * | 2017-10-13 | 2019-04-15 | Hublot Sa Geneve | Alloy with high entropy. |
JP7471078B2 (en) | 2019-12-24 | 2024-04-19 | 山陽特殊製鋼株式会社 | A multi-component alloy with excellent resistance to softening, balance of strength and elongation, and excellent wear resistance. |
EP4060425A1 (en) | 2021-03-16 | 2022-09-21 | Nivarox-FAR S.A. | Hairspring for timepiece movement |
US20220307114A1 (en) * | 2021-03-23 | 2022-09-29 | City University Of Hong Kong | High entropy alloy, method of preparation and use of the same |
CN114058888B (en) * | 2021-10-25 | 2022-07-05 | 重庆大学 | Smelting method of FeCrCoNiAl high-entropy alloy |
CN115121801B (en) * | 2022-06-15 | 2023-06-23 | 中国人民解放军陆军装甲兵学院 | Laser additive repairing method for iron-based material damaged part and repairing powder adopted by same |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
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GB647783A (en) * | 1947-05-03 | 1950-12-20 | Elgin Nat Watch Co | Process of making power springs and other articles of high elastic strength |
CH299223A (en) * | 1952-01-14 | 1954-05-31 | Reinhard Dr Straumann | Process for the production of a mainspring for watches and mainspring obtained by this process. |
FR1151350A (en) * | 1955-06-11 | 1958-01-29 | Genevoise Degrossissage D Or | Stainless alloy with high resistance to fatigue and deformation and spring for watch movement in this alloy |
US3928085A (en) * | 1972-05-08 | 1975-12-23 | Suwa Seikosha Kk | Timepiece mainspring of cobalt-nickel base alloys having high elasticity and high proportional limit |
CH621577A5 (en) * | 1976-07-15 | 1981-02-13 | Straumann Inst Ag | |
EP1039352B1 (en) * | 1999-03-26 | 2003-10-08 | Rolex Sa | Self-compensating spring for clockwork movement spring balance and method for treating the same |
JP2005527699A (en) * | 2001-12-14 | 2005-09-15 | エイティーアイ・プロパティーズ・インコーポレーテッド | Method for treating beta-type titanium alloy |
JP2005140674A (en) * | 2003-11-07 | 2005-06-02 | Seiko Epson Corp | Spring, spiral spring and hair spring for watch, and watch |
FR2905707B1 (en) * | 2006-09-08 | 2009-01-23 | Centre Nat Rech Scient | PROCESS FOR DEPOSITING ON A SUBSTRATE A THIN LAYER OF METAL ALLOY AND METAL ALLOY IN THE FORM OF A THIN LAYER. |
CN101320617A (en) * | 2007-06-08 | 2008-12-10 | 财团法人工业技术研究院 | Soft magnetic film inductor and magnetic multi-component alloy thin film |
TWI347978B (en) * | 2007-09-19 | 2011-09-01 | Ind Tech Res Inst | Ultra-hard composite material and method for manufacturing the same |
WO2010055943A1 (en) * | 2008-11-17 | 2010-05-20 | 財団法人電気磁気材料研究所 | High-hardness constant-modulus alloy insensitive to magnetism, process for producing same, balance spring, mechanical driving device, and watch |
CN102776430B (en) * | 2012-08-20 | 2014-08-06 | 太原理工大学 | AlCoCrFeNiTix high-entropy alloy material and method for preparing same |
CN102787266A (en) * | 2012-09-04 | 2012-11-21 | 四川大学 | Titanium carbonitride based metal ceramic based on high-entropy alloy binder phase and preparation method of metal ceramic |
CN102796933A (en) * | 2012-09-04 | 2012-11-28 | 四川大学 | High-entropy alloy binder phase-based nitrogen-containing hard alloy and preparation method thereof |
CN103194656A (en) * | 2013-04-19 | 2013-07-10 | 梧州漓佳铜棒有限公司 | AlxCrFeNiCuVTi high-entropy alloy material and preparation method thereof |
EP2813906A1 (en) * | 2013-06-12 | 2014-12-17 | Nivarox-FAR S.A. | Part for clockwork |
CN103556146B (en) * | 2013-11-06 | 2016-01-20 | 四川建筑职业技术学院 | Prepare the method for high-entropy alloy coating |
CN104651828B (en) * | 2013-11-22 | 2017-06-06 | 沈阳工业大学 | A kind of ferrous alloy surface prepares high-entropy alloy-base composite material modified layer powder |
JP6459272B2 (en) * | 2014-07-23 | 2019-01-30 | 日立金属株式会社 | Alloy structure |
KR101728936B1 (en) * | 2014-07-28 | 2017-04-21 | 세종대학교산학협력단 | High entropy alloy having excellent strength and ductility |
CN104213013B (en) * | 2014-09-28 | 2016-09-21 | 哈尔滨工业大学 | A kind of TiZrNbMoxhfymany pivots high temperature alloy and preparation method thereof |
CN105671392B (en) * | 2014-11-19 | 2017-11-03 | 北京科技大学 | A kind of TiZrHfNb base high-entropy alloys of nitrogen reinforcing and preparation method thereof |
US10190197B2 (en) | 2015-12-11 | 2019-01-29 | The Trustees Of Dartmouth College | Oxidation resistant high-entropy alloys |
CN105950946B (en) * | 2016-07-01 | 2017-11-21 | 广西大学 | A kind of method that high-entropy alloy composition design is carried out based on segregation situation between constituent element |
-
2016
- 2016-09-30 EP EP16191867.7A patent/EP3301520A1/en not_active Withdrawn
-
2017
- 2017-07-28 US US16/331,038 patent/US20190235441A1/en not_active Abandoned
- 2017-07-28 EP EP17745346.1A patent/EP3519900B1/en active Active
- 2017-07-28 RU RU2019112854A patent/RU2715832C1/en active
- 2017-07-28 WO PCT/EP2017/069219 patent/WO2018059795A1/en unknown
- 2017-07-28 JP JP2019513437A patent/JP6892914B2/en active Active
- 2017-07-28 CN CN201780059624.2A patent/CN109804321B/en active Active
-
2020
- 2020-01-29 US US16/775,657 patent/US11042120B2/en active Active
-
2021
- 2021-02-17 US US17/177,426 patent/US20210263470A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
JP2019534378A (en) | 2019-11-28 |
US20190235441A1 (en) | 2019-08-01 |
US20210263470A1 (en) | 2021-08-26 |
WO2018059795A1 (en) | 2018-04-05 |
JP6892914B2 (en) | 2021-06-23 |
US20200241475A1 (en) | 2020-07-30 |
RU2715832C1 (en) | 2020-03-03 |
EP3301520A1 (en) | 2018-04-04 |
CN109804321B (en) | 2021-07-27 |
CN109804321A (en) | 2019-05-24 |
US11042120B2 (en) | 2021-06-22 |
EP3519900B1 (en) | 2021-05-05 |
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