EP3070182B1 - Weissgoldlegierung - Google Patents

Weissgoldlegierung Download PDF

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Publication number
EP3070182B1
EP3070182B1 EP15159421.5A EP15159421A EP3070182B1 EP 3070182 B1 EP3070182 B1 EP 3070182B1 EP 15159421 A EP15159421 A EP 15159421A EP 3070182 B1 EP3070182 B1 EP 3070182B1
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EP
European Patent Office
Prior art keywords
free
gold alloy
alloy
alloy according
expressed
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.)
Active
Application number
EP15159421.5A
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English (en)
French (fr)
Other versions
EP3070182A1 (de
Inventor
Denis Vincent
Polychronis Nakis Karapatis
Gregory Kissling
Stéphane Lauper
Gaëtan Villard
Alban Dubach
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Swatch Group Research and Development SA
Original Assignee
Swatch Group Research and Development SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Priority to EP15159421.5A priority Critical patent/EP3070182B1/de
Priority to US15/052,011 priority patent/US11591672B2/en
Priority to JP2016046671A priority patent/JP6280580B2/ja
Priority to CN201610146929.4A priority patent/CN105986142B/zh
Priority to RU2016109478A priority patent/RU2016109478A/ru
Publication of EP3070182A1 publication Critical patent/EP3070182A1/de
Application granted granted Critical
Publication of EP3070182B1 publication Critical patent/EP3070182B1/de
Priority to JP2017222556A priority patent/JP6827909B2/ja
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C27/00—Making jewellery or other personal adornments
    • A44C27/001—Materials for manufacturing jewellery
    • A44C27/002—Metallic materials
    • A44C27/003—Metallic alloys
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • A—HUMAN NECESSITIES
    • A44—HABERDASHERY; JEWELLERY
    • A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
    • A44C5/00—Bracelets; Wrist-watch straps; Fastenings for bracelets or wrist-watch straps
    • A44C5/18—Fasteners for straps, chains or the like
    • 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
    • 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

Definitions

  • the present invention relates to a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free, and manganese-free alloy.
  • the invention also relates to a timepiece, jewelery or jewelery comprising at least one component made with such an alloy.
  • the gray gold alloys for use in the watch and jewelery fields must meet two constraints relating, on the one hand, to their brightness and whiteness and, on the other hand, to their deformation capacity. They must have a color and a brightness of pure whiteness and excellent ductility and corrosion resistance. More particularly, the desired white gold alloys must have values according to the chromatic model L * a * b (CIE 1976) such that L ⁇ 80, a * ⁇ 1.5 and b * ⁇ 7, preferably b * ⁇ 6, and preferably b * ⁇ 5, and an HV hardness of between 140 Hv and 225 Hv, the lowest values being the most favorable to the deformation.
  • L * a * b CIE 1976
  • This rhodium-plating operation has a major disadvantage in the long term because the layer of rhodium deposited on the order of 1 to 5 microns always ends up wearing. As a result, the after-sales service is confronted with an expensive reworking operation because of the need to mask the difference in color between the alloy and the rhodium refining layer.
  • the patent EP 0 346 595 refers to alloys having 60-85% Au, 4-20% Pt, 2-20% Pd, 1-11 Ag, and 0.1-3% Ir / Rh.
  • the patent EP 1 010 768 refers to 18 carat white gold alloys having a palladium content of between 12 and 14%, and also including copper, which gives color values in the L, a *, b * system such that 1.8 ⁇ a * ⁇ 2.3 and 7 ⁇ b * ⁇ 10.
  • the patent EP 1 227 166 refers to palladium-free 18K white gold alloys, including copper and manganese, giving color values in the L, a *, b * system such that 2.6 ⁇ a * ⁇ 6 and 10 ⁇ b * ⁇ 13.
  • the patent EP 1,245,688 refers to 18-carat white gold alloys having a palladium content of between 5 and 7%, also including copper and silver, giving chromatic values in the L, a *, b * system that 1.5 ⁇ a * ⁇ 4.5 and 10.5 ⁇ b * ⁇ 15.2.
  • alloys described in these three patents chromatically have values of a * and b * too high to claim to avoid an improvement of the surface by a rhodium.
  • the patent application EP 2 546 371 refers to gold alloys 18-carat gray with a palladium content between 2 and 12% and a chromium content of between 13 and 23%, which gives chromatic values in the system L, a *, b * such that 0.25 ⁇ a * ⁇ 0.7 and 3 ⁇ b * ⁇ 4.2.
  • the patent application WO 2010/127458 relates to 18-carat white gold alloys having a palladium content of between 18 and 24% and a content of various elements including Zr, Nb or Mn of between 1 and 6%, which gives chromatic values in the system L, a *, b * such that 1.1 ⁇ a * ⁇ 1.5 and 4.5 ⁇ b * ⁇ 5.7.
  • alloys described in these last two patent applications chromatically have values of a * and b * sufficient to claim to avoid an improvement of the surface by a rhodium.
  • these alloys have a hardness too high (see alloys No. 2 (370 Hv) and 3 (276 Hv) Tables 1 and 2 below) to ensure ease of use during manufacturing deformations.
  • the object of the present invention is therefore to substantially improve the gray-gold alloys by providing a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free alloy, and without manganese, to eliminate rhodium without reducing its deformability properties.
  • the object of the present invention is therefore to substantially improve the gray-gold alloys by providing a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free, and non-nickel free gold alloy.
  • manganese whose deformability allows its transformation by rolling techniques and cold drawing without risk of cracking and which is economical to achieve.
  • Another object of the present invention is to provide a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free, and manganese-free gold alloy.
  • Another object of the present invention is to provide a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free, and manganese-free gold alloy which can be easily polished and great whiteness after polishing.
  • the present invention relates to a nickel-free, cobalt-free, iron-free, silver-free, copper-free, zirconium-free, niobium-free, chromium-free and manganese-free gold alloy comprising, expressed by weight, 75.0 to 76.5% Au, 15 to 23% Pd, 0.5 to 5% Rh, 0 to 7% Pt, and 0 to 5% of at least one of the Ir addition elements, Ru, Ti, In, Ga, B and Re, the respective percentages of all elements of the alloy completing up to 100%.
  • a gray gold alloy is obtained which satisfies all the criteria required for alloys intended to be used in the watch and jewelery fields, in particular with regard to its color and its brilliance. as well as its ability to be cold deformed without risk of cracking. In addition, there is excellent resistance to corrosion.
  • the present invention also relates to a timepiece, jewelery or jewelery comprising at least one component made of an alloy as defined above.
  • This component is for example a watch case, a dial, a bracelet, a bracelet clasp, a jewel, or an accessory.
  • the present invention also relates to the use of an alloy as defined above in a timepiece, jewelery or jewelery.
  • the alloy of the present invention is a gray gold alloy, nickel free, cobalt free, iron free, silver free, copper free, manganese free, zirconium free, chromium free, and niobium free.
  • the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 15 to 23% of Pd, from 0.5 to 5% of Rh , from 0 to 7% of Pt, and from 0 to 5% of at least one of the Ir, Ru, Ti, In, Ga, B and Re additive elements, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 0.5 and 7%.
  • the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 17 to 22.5% of Pd, from 0.5 to 4% of Rh , from 0 to 6% of Pt, and from 0 to 5% of at least one of the Ir, Ru, Ti, In, Ga, B and Re additive elements, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 0.5 and 6%.
  • the gold alloy is an 18-carat alloy and has, expressed by weight, 75.0 to 76.5% Au, 18 to 22.5% Pd, 1.5 and 3% of Rh, from 0 to 4% of Pt, and from 0 to 4% of at least one of the addition elements Ir, Ru, Ti, In, Ga, B and Re, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 1 and 4%.
  • the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 19 to 22% of Pd, from 1.5 to 3% of Rh , from 0 to 4.5% of Pt, and from 0 to 4.5% of at least one of the Ir, Ru, Ti, In, Ga, B and Re addition elements, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 1 and 4.5%.
  • the gold alloy is an 18-carat alloy and comprises, expressed by weight, from 75.0 to 76.5% of Au, from 19 to 21.5% of Pd, from 1.5 to 3% of Rh , from 0 to 4% of Pt, and from 0 to 4% of at least one of the Ir, Ru, Ti, In, Ga, B and Re additive elements, the respective percentages of all the elements of the alloy completing up to 100%. If the platinum is present, its percentage is between 1 and 4%.
  • the gold alloy comprises at least one of the elements Ir, Ti, in a proportion for each element of between 0.002 and 1% by weight.
  • the proportion of Ir is preferably between 0.01 and 1% by weight.
  • the proportion of Ti is preferably between 20 and 500 ppm.
  • the proportion of Re is preferably between 0.002 and 1% by weight, and preferably close to 0.002% by weight.
  • the proportion of indium is preferably between 1 and 4% by weight.
  • the proportion of Ga is preferably between 0.2 and 2% by weight.
  • the proportion of B is preferably between 0.002 and 1% by weight, and more preferably between 0.005 and 0.03% by weight.
  • the proportion of Ru is preferably between 0.002 and 1% by weight, and more preferably between 0.008 and 0.015% by weight.
  • the gold alloys according to the invention find a particular application for the realization of a timepiece of jewelery or jewelery.
  • this alloy makes it possible in particular to avoid the galvanic deposition of rhodium which is commonly used in the watchmaking and jeweler 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 hardening rate between each annealing is 66 to 80%.
  • Each anneal lasts 20 to 30 minutes and is at 900 ° C under a reducing atmosphere composed of N 2 and H 2 .
  • the cooling between annealing is done by quenching with water.
  • Table 1 No. At. Pd. Pt. Rh. Ag. Ga. Fe. B. Cu. Ru. Ir. Cr. Min. Zr. Nb. In. Ti.
  • Table 2 gives in particular the indications relating to the Vickers hardness of the alloy in the annealed state, as well as to those of the color measured in a three-axis coordinate system.
  • CIELab CIE being the acronym of the International Commission for Lighting and Lab the three coordinate axes
  • AXA measuring the red-green component
  • blue negative value -b
  • Alloy No. 1 is Au binary alloy, 18 carats Pd.
  • Alloys Nos. 2 and 3 are alloys of the prior art and have the disadvantage of having too high a hardness.
  • Alloy No. 22 is the colorimetric reference of rhodium.
  • the 18-carat white gold alloys of the invention were developed and deformed to meet the dual brightness / whiteness and deformation capacity requirements for alloys for use in the watch and watchmaking industries.
  • jewelery or to present the color values such as L ⁇ 80, a * ⁇ 1.5 and b * ⁇ 5, and a HV hardness of between 140 Hv and 225 Hv, and preferably between 140 Hv and 180 Hv.
  • the alloys of the comparative examples do not make it possible to respond to this double constraint.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Adornments (AREA)
  • Catalysts (AREA)

Claims (17)

  1. Graugoldlegierung ohne Nickel, ohne Kobalt, ohne Eisen, ohne Silber, ohne Kupfer, ohne Zirkonium, ohne Niob, ohne Chrom und ohne Mangan, die die folgenden Elemente enthält:
    75,0 bis 76,5 Gew.-% Au
    15 bis 23 Gew.-% Pd,
    0,5 bis 5 Gew.-% Rh,
    0 bis 7 Gew.-% Pt,
    0 bis 5 Gew.-% mindestens eines der Zusatz-Elemente Ir, Ru, Ti, In, Ga, B und Re,
    wobei sich die jeweiligen Prozentsätze der Gesamtheit der Elemente der Legierung auf 100 % ergänzen.
  2. Graugoldlegierung nach Anspruch 1, die 0,5 bis 7 Gew.-% Pt enthält.
  3. Graugoldlegierung nach Anspruch 1, die 75,0 bis 76,5 Gew.-% Au, 17 bis 22,5 Gew.-% Pd, 0,5 bis 4 Gew.-% Rh, 0 bis 6 Gew.-% Pt und 0 bis 5 Gew.-% mindestens eines der Zusatz-Elemente Ir, Ru, Ti, In, Ga, B und Re enthält, wobei sich die jeweiligen Prozentsätze der Gesamtheit der Elemente der Legierung auf 100 % ergänzen.
  4. Graugoldlegierung nach Anspruch 3, die 0,5 bis 6 Gew.-% Pt enthält.
  5. Graugoldlegierung nach Anspruch 1, die 75,0 bis 76,5 Gew.-% Au, 18 bis 22,5 Gew.-% Pd, 1,5 bis 3 Gew.-% Rh, 0 bis 4 Gew.-% Pt und 0 bis 4 Gew.-% mindestens eines der Zusatz-Elemente Ir, Ru, Ti, In, Ga, B und Re enthält, wobei sich die jeweiligen Prozentsätze der Gesamtheit der Elemente der Legierung auf 100 % ergänzen.
  6. Graugoldlegierung nach Anspruch 5, die 1 bis 4 Gew.-% Pt enthält.
  7. Graugoldlegierung nach Anspruch 1, die 75,0 bis 76,5 Gew.-% Au, 19 bis 22 Gew.-% Pd, 1,5 bis 3 Gew.-% Rh, 0 bis 4,5 Gew.-% Pt und 0 bis 4,5 Gew.-% mindestens eines der Zusatz-Elemente Ir, Ru, Ti, In, Ga, B und Re enthält, wobei sich die jeweiligen Prozentsätze der Gesamtheit der Elemente der Legierung auf 100 % ergänzen.
  8. Graugoldlegierung nach Anspruch 7, die ein 1 bis 4,5 Gew.-% Pt enthält.
  9. Graugoldlegierung nach Anspruch 1, die 75,0 bis 76,5 Gew.-% Au, 19 bis 21,5 Gew.-% Pd, 1,5 bis 3 Gew.-% Rh, 0 bis 4 Gew.-% Pt und 0 bis 4 Gew.-% mindestens eines der Zusatz-Elemente Ir, Ru, Ti, In, Ga, B und Re enthält, wobei sich die jeweiligen Prozentsätze der Gesamtheit der Elemente der Legierung auf 100 % ergänzen.
  10. Graugoldlegierung nach Anspruch 9, die 1 bis 4 Gew.-% Pt enthält.
  11. Legierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass sie mindestens eines der Elemente Ir, Ti in einem Anteil jedes Elements, der im Bereich von 0,002 bis 1 Gew.-% liegt, enthält.
  12. Legierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es Ti in einem Bereich von 20 bis 500 ppm enthält.
  13. Legierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es Ir in einem Bereich von 0,01 bis 1 Gew.-% enthält.
  14. Legierung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass es In in einem Bereich von 1 bis 4 Gew.-% enthält.
  15. Zeitmessgerät, Schmuckteil oder Juwelierteil, das mindestens eine Komponente enthält, die aus einer Legierung nach einem der Ansprüche 1 bis 14 hergestellt ist.
  16. Zeitmessgerät, Schmuckstück oder Juwelierartikel nach Anspruch 15, dadurch gekennzeichnet, dass die Komponente aus der Gruppe gewählt ist, die ein Uhrengehäuse, ein Zifferblatt, ein Armband, eine Armbandschließe, ein Schmuckstück und ein Accessoire enthält.
  17. Verwendung einer Legierung nach einem der Ansprüche 1 bis 14 in einem Zeitmessgerät, einem Schmuckstück oder einem Juwelierartikel.
EP15159421.5A 2015-03-17 2015-03-17 Weissgoldlegierung Active EP3070182B1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP15159421.5A EP3070182B1 (de) 2015-03-17 2015-03-17 Weissgoldlegierung
US15/052,011 US11591672B2 (en) 2015-03-17 2016-02-24 Grey gold alloy
JP2016046671A JP6280580B2 (ja) 2015-03-17 2016-03-10 グレーゴールド合金
CN201610146929.4A CN105986142B (zh) 2015-03-17 2016-03-15 灰金合金
RU2016109478A RU2016109478A (ru) 2015-03-17 2016-03-16 Сплав серого золота
JP2017222556A JP6827909B2 (ja) 2015-03-17 2017-11-20 グレーゴールド合金

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP15159421.5A EP3070182B1 (de) 2015-03-17 2015-03-17 Weissgoldlegierung

Publications (2)

Publication Number Publication Date
EP3070182A1 EP3070182A1 (de) 2016-09-21
EP3070182B1 true EP3070182B1 (de) 2017-08-30

Family

ID=52779485

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15159421.5A Active EP3070182B1 (de) 2015-03-17 2015-03-17 Weissgoldlegierung

Country Status (5)

Country Link
US (1) US11591672B2 (de)
EP (1) EP3070182B1 (de)
JP (2) JP6280580B2 (de)
CN (1) CN105986142B (de)
RU (1) RU2016109478A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024134394A1 (fr) * 2022-12-20 2024-06-27 Manufacture D'horlogerie Audemars Piguet Sa Procédé pour la fabrication d'un composant horloger à base d'alliage d'or et pièce résultante

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3070182B1 (de) * 2015-03-17 2017-08-30 The Swatch Group Research and Development Ltd. Weissgoldlegierung
WO2018013560A1 (en) * 2016-07-12 2018-01-18 Mancini Christina M Hypoallergenic earrings
EP3339455B1 (de) * 2016-12-20 2020-02-05 Montres Breguet S.A. Weissgoldlegierung
WO2019077819A1 (ja) 2017-10-19 2019-04-25 株式会社デンソー 車両用位置判定システム
JP6789528B1 (ja) * 2019-09-26 2020-11-25 田中貴金属工業株式会社 医療用Ａｕ−Ｐｔ−Ｐｄ合金
EP3808865B1 (de) 2019-10-17 2023-01-18 Richemont International S.A. Weissgoldlegierung und ihr herstellungsverfahren
US11268174B1 (en) * 2021-06-10 2022-03-08 Chow Sang Sang Jewellery Company Limited Jewelry alloy
EP4421194A1 (de) 2023-02-23 2024-08-28 Richemont International S.A. Graugoldlegierung
CN116987926B (zh) * 2023-08-09 2025-10-28 深圳市熠辉金珠宝有限公司 K金弹簧及其制备方法
CN118676096B (zh) * 2024-05-07 2025-05-06 深圳中宝新材科技有限公司 一种金合金键合丝及其制备方法

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EP2546371B1 (de) 2011-07-12 2016-12-21 Cendres + Métaux SA Weißgold, 18 Karat
EP3070182B1 (de) * 2015-03-17 2017-08-30 The Swatch Group Research and Development Ltd. Weissgoldlegierung
EP3339455B1 (de) * 2016-12-20 2020-02-05 Montres Breguet S.A. Weissgoldlegierung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024134394A1 (fr) * 2022-12-20 2024-06-27 Manufacture D'horlogerie Audemars Piguet Sa Procédé pour la fabrication d'un composant horloger à base d'alliage d'or et pièce résultante

Also Published As

Publication number Publication date
CN105986142B (zh) 2018-09-14
RU2016109478A (ru) 2017-09-21
RU2016109478A3 (de) 2019-09-09
JP6827909B2 (ja) 2021-02-10
JP6280580B2 (ja) 2018-02-14
CN105986142A (zh) 2016-10-05
US20160273077A1 (en) 2016-09-22
JP2018048409A (ja) 2018-03-29
US11591672B2 (en) 2023-02-28
JP2016172925A (ja) 2016-09-29
EP3070182A1 (de) 2016-09-21

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