EP3519900B1 - Timepiece component having a high-entropy alloy - Google Patents

Timepiece component having a high-entropy alloy Download PDF

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Publication number
EP3519900B1
EP3519900B1 EP17745346.1A EP17745346A EP3519900B1 EP 3519900 B1 EP3519900 B1 EP 3519900B1 EP 17745346 A EP17745346 A EP 17745346A EP 3519900 B1 EP3519900 B1 EP 3519900B1
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Prior art keywords
entropy alloy
following formula
comprised
timepiece component
high entropy
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German (de)
French (fr)
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EP3519900A1 (en
Inventor
Christian Charbon
Guido Plankert
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Nivarox Far SA
Nivarox SA
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Nivarox Far SA
Nivarox SA
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    • 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

Description

DOMAINE TECHNIQUETECHNICAL AREA

La présente invention concerne un composant horloger comportant un alliage haute entropie, ainsi qu'un procédé de fabrication d'un tel composant horloger. L'invention concerne également l'utilisation d'un alliage haute entropie pour fabriquer un composant horloger.The present invention relates to a timepiece component comprising a high entropy alloy, as well as to a method of manufacturing such a timepiece component. The invention also relates to the use of a high entropy alloy for manufacturing a watch component.

ART ANTERIEURPRIOR ART

Les composants horlogers, et particulièrement les ressorts de barillet, sont soumis à de fortes contraintes, notamment au cours de leurs procédés de fabrication, mais aussi pendant leur utilisation.Watchmaking components, and particularly barrel springs, are subjected to high stresses, in particular during their manufacturing processes, but also during their use.

Ils doivent notamment présenter une résistance mécanique élevée et une grande ductilité. Or actuellement, les composants horlogers présentent rarement simultanément ces caractéristiques antagonistes. On connaît par exemple le brevet GB 647 783 A , qui divulgue des composants horlogers dans des alliages haute entropie comportant du Fe, Mn, Co, Cr en outres.They must in particular exhibit high mechanical strength and high ductility. Now, watch components rarely simultaneously exhibit these antagonistic characteristics. We know for example the patent GB 647 783 A , which discloses watch components in high entropy alloys comprising Fe, Mn, Co, Cr in addition.

RESUME DE L'INVENTIONSUMMARY OF THE INVENTION

L'invention vise à remédier aux inconvénients de l'état de la technique en proposant un composant horloger présentant une résistance mécanique plus élevée et une plus grande ductilité.The invention aims to remedy the drawbacks of the state of the art by proposing a watch component exhibiting higher mechanical strength and greater ductility.

Pour ce faire, est proposé selon un premier aspect de l'invention, un composant horloger comportant un alliage haute entropie, l'alliage haute entropie comportant entre 4 et 13 éléments principaux formant une unique solution solide, l'alliage haute entropie présentant une concentration en chaque élément principal comprise entre 1 et 55 % atomique. En effet, un tel composant présente une plus grande résistance mécanique et une plus grande ductilité que ceux de l'art antérieur.To do this, is proposed according to a first aspect of the invention, a watch 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 principal element between 1 and 55 atomic%. Indeed, such component exhibits greater mechanical strength and greater ductility than those of the prior art.

Avantageusement, la concentration en chaque élément principal est comprise entre 10 et 55 % atomique.Advantageously, the concentration of each main element is between 10 and 55 atomic%.

Selon différents modes de réalisation préférentiels:

  • l'alliage haute entropie peut répondre à la formule suivante : FeaMnbCocCrd dans laquelle a, b, c et d sont compris entre 1 et 55 % atomique;
  • l'alliage haute entropie peut présenter la formule suivante : Fe50Mn30Co10Cr10 ;
  • l'alliage haute entropie peut répondre à la formule suivante: Fe80-xMnxCo10Cr10, avec x compris entre 25 et 79% atomique, et de préférence x compris entre 25 et 45% atomique;
  • l'alliage haute entropie peut répondre à la formule suivante : FeaMnbNieCocCrd dans laquelle a, b, c, d et e sont compris entre 1 et 55 % atomique ;
  • l'alliage haute entropie peut répondre à la formule suivante Fe20Mn20Ni20Co20Cr20 ;
  • l'alliage haute entropie peut répondre à la formule suivante Fe40Mn27Ni26Co5Cr2 ;
  • l'alliage haute entropie peut répondre à la formule suivante : TaaNbbHfcZrdCre dans laquelle a, b, c, d et e sont compris entre 1 et 55 % atomique;
  • l'alliage haute entropie peut en particulier répondre à la formule suivante Ta20Nb20Hf20Zr20Ti20 ;
  • l'alliage haute entropie peut répondre à la formule suivante : AlaLibMgcScdTie dans laquelle a, b, c, d et e sont compris entre 1 et 55 % atomique ;
  • l'alliage haute entropie peut en particulier répondre à la formule suivante Al20Li20Mg10Sc20Ti30 ;
  • l'alliage haute entropie peut répondre à la formule suivante : AlaCobCrcCudFeeNif dans laquelle a, b, c, d, e et f sont compris entre 1 et 55 % atomique.
  • l'alliage haute entropie peut répondre à la formule suivante Cr18.2Fe18.2Co18.2Ni18.2Cu18.2Al9.0
According to different preferred embodiments:
  • the high entropy alloy can correspond to the following formula: Fe a Mn b Co c Cr d in which a, b, c and d are between 1 and 55 atomic%;
  • the high entropy alloy can have the following formula: Fe 50 Mn 30 Co 10 Cr 10 ;
  • the high entropy alloy can correspond to the following formula: Fe 80 - x Mn x Co 10 Cr 10 , with x between 25 and 79 atomic%, and preferably x between 25 and 45 atomic%;
  • the high entropy alloy can correspond to the following formula: Fe a Mn b Ni e Co c Cr d in which a, b, c, d and e are between 1 and 55 atomic%;
  • the high entropy alloy can correspond to the following formula Fe 20 Mn 20 Ni 20 Co 20 Cr 20 ;
  • the high entropy alloy can correspond to the following formula Fe 40 Mn 27 Ni 26 Co 5 Cr 2 ;
  • the high entropy alloy can correspond to the following formula: Ta a Nb b Hf c Zr d Cr e in which a, b, c, d and e are between 1 and 55 atomic%;
  • the high entropy alloy can in particular correspond to the following formula Ta 20 Nb 20 Hf 20 Zr 20 Ti 20 ;
  • the high entropy alloy can correspond to the following formula: Al a Li b Mg c Sc d Ti e in which a, b, c, d and e are between 1 and 55 atomic%;
  • the high entropy alloy can in particular correspond to the following formula Al 20 Li 20 Mg 10 Sc 20 Ti 30 ;
  • the high entropy alloy can correspond to the following formula: Al a Co b Cr c Cu d Fe e Ni f in which a, b, c, d, e and f are between 1 and 55 atomic%.
  • the high entropy alloy can meet the following formula Cr 18.2 Fe 18.2 Co 18.2 Ni 18.2 Cu 18.2 Al 9.0

Avantageusement, l'alliage haute entropie peut comporter un ou plusieurs éléments interstitiels parmi les suivants : C, N, B. Ces éléments interstitiels permettent d'augmenter encore la résistance mécanique de l'alliage.Advantageously, the high entropy alloy can 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.

Avantageusement, l'alliage haute entropie peut comporter un ou plusieurs éléments de durcissement structural parmi les suivants :Ti, Al, Be, Nb, de préférence dans une concentration massique comprise entre 0.1 et 3%.Advantageously, the high entropy alloy can comprise one or more structural hardening elements from among the following: Ti, Al, Be, Nb, preferably in a mass concentration of between 0.1 and 3%.

Selon différents modes de réalisation, le composant horloger peut être un des suivants: un ressort, un ressort de barillet, un ressort sautoir, une cheville, un plateau, une ancre, une tige, une baguette d'ancre, une fourchette d'ancre, une roue, une roue d'échappement, un arbre, un pignon, une masse oscillante, une tige de remontoir, une couronne, une boite de montre, un maillon de bracelet, une lunette de montre, un fermoir de bracelet.According to different embodiments, the horological component can be one of the following: a spring, a barrel spring, a jumper spring, a pin, a plate, an anchor, a rod, an anchor stick, 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.

Un deuxième aspect de l'invention concerne également l'utilisation d'un alliage haute entropie pour fabriquer un composant horloger, l'alliage haute entropie comportant entre 4 et 13 éléments principaux formant une unique solution solide, l'alliage présentant une concentration en chaque élément principal comprise entre 1 et 55 % atomique.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%.

BREVE DESCRIPTION DES FIGURESBRIEF DESCRIPTION OF THE FIGURES

D'autres caractéristiques et avantages de la présente invention apparaîtront plus clairement dans la description détaillée suivante des modes de réalisation préférés, présentés à titre d'exemple non limitatifs en référence aux figures annexées, parmi lesquelles:

  • la figure 1 représente schématiquement un ressort de barillet selon un mode de réalisation de l'invention ;
  • la figure 2 représente schématiquement les étapes d'un procédé de fabrication d'un ressort de barillet selon un mode de réalisation de l'invention.
Other characteristics and advantages of the present invention will emerge more clearly in the following detailed description of the preferred embodiments, presented by way of non-limiting example with reference to the appended figures, among which:
  • the figure 1 schematically shows a barrel spring according to one embodiment of the invention;
  • the figure 2 schematically represents the steps of a method of manufacturing a barrel spring according to one embodiment of the invention.

DESCRIPTION DETAILLEEDETAILED DESCRIPTION

La figure 1 représente un ressort de barillet 1 selon un mode de réalisation. Ce ressort de barillet 1 est réalisé dans un alliage haute entropie.The figure 1 shows a barrel spring 1 according to one embodiment. This barrel spring 1 is made from a high entropy alloy.

Dans un tel alliage haute entropie, l'entropie de mélange est élevée et elle rend thermodynamiquement plus stable la phase unique que le mélange de plusieurs phases.In such a high entropy alloy, the mixing entropy is high and it makes the single phase thermodynamically more stable than the mixing of several phases.

Le ressort de barillet est de préférence réalisé dans l'alliage haute entropie décrit dans la publication " Metastable high-entropy dual-phase alloys overcome the strength-ductility trade-off", Zhiming Li et al, Nature 534, 227-230 (09 June 2016 ). Cet alliage haute entropie présente la formule suivante: Fe80-xMnxCo10Cr10. x est de préférence compris entre 25 et 79% atomique.The barrel spring is preferably made from 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: Fe 80-x Mn x Co 10 Cr 10 . x is preferably between 25 and 79 atomic%.

Plus précisément, selon un premier mode de réalisation, le ressort de barillet peut être réalisé dans un alliage Fe35Mn45Co10Cr10. Le ressort de barillet ainsi réalisé présente l'avantage de combiner une haute limite à la rupture et une grande ductilité.More precisely, according to a first embodiment, the barrel spring can be made from an Fe 35 Mn 45 Co 10 Cr 10 alloy. The barrel spring thus produced has the advantage of combining a high tensile strength and high ductility.

Selon un deuxième mode de réalisation, le ressort de barillet peut être réalisé dans un alliage Fe40Mn40Co10Cr10. Le ressort ainsi réalisé présente l'avantage d'avoir une grande résistance à la rupture et une grande ductilité. Il fonctionne en outre suivant un mécanisme TWIP (« twinning induced plasticity »).According to a second embodiment, the barrel spring can be made from an Fe 40 Mn 40 Co 10 Cr 10 alloy. The spring thus produced presents the advantage of having a high tensile strength and high ductility. It also works according to a TWIP (“twinning induced plasticity”) mechanism.

Selon un troisième mode de réalisation, le ressort de barillet peut être réalisé dans un alliage Fe45Mn35Co10Cr10. Le ressort de barillet ainsi réalisé présente l'avantage d'avoir encore une plus grande résistance à la rupture et une plus grande ductilité. Il fonctionne en outre suivant un mécanisme TRIP (« transformation induced plasticity »).According to a third embodiment, the barrel spring can be made from an Fe 45 Mn 35 Co 10 Cr 10 alloy. The barrel spring thus produced has the advantage of having even greater breaking strength and greater ductility. It also works according to a TRIP mechanism (“transformation induced plasticity”).

Selon un quatrième mode de réalisation, le ressort de barillet peut être réalisé dans un alliage Fe50Mn30Co10Cn10.Le ressort de barillet ainsi réalisé présente l'avantage d'avoir encore une plus grande résistance à la rupture et une plus grande ductilité. Il fonctionne selon un mécanisme TRIP avec l'apparition de deux phases, cfc et hc, par un mécanisme de mâclage.According to a fourth embodiment, the barrel spring can be made from an Fe 50 Mn 30 Co 10 Cn 10 alloy. The barrel spring thus produced has the advantage of having even greater resistance to breaking and greater resistance to breaking. high ductility. It works according to a TRIP mechanism with the appearance of two phases, cfc and hc, by a twisting mechanism.

L'invention n'est pas limitée à la fabrication d'un ressort de barillet. En effet, d'autres composants horlogers pourraient être fabriqués dans l'alliage haute entropie Fe80-xMnxCo10Cr10, comme un ressort, une tige, une cheville, un balancier, un axe, un plateau, une ancre, une baguette d'ancre, une fourchette d'ancre, une roue d'échappement, un arbre, un pignon, une masse oscillante, une tige de remontoir, une couronne, un ressort sautoir, une boite de montre, un maillon de bracelet, une lunette de montre, un fermoir de bracelet...The invention is not limited to the manufacture of a barrel spring. Indeed, other watch components could be manufactured in the high entropy alloy Fe 80-x Mn x Co 10 Cr 10 , such as a spring, a rod, a pin, a balance, an axis, a plate, an anchor, etc. an anchor stick, an anchor fork, an escape wheel, a shaft, a pinion, an oscillating weight, a winding stem, a crown, a jumper spring, a watch case, a bracelet link, a watch bezel, a bracelet clasp ...

La figure 2 représente schématiquement les étapes d'un procédé de fabrication du ressort de barillet de la figure 1.The figure 2 schematically represents the steps of a manufacturing process of the barrel spring of the figure 1 .

Ce procédé comporte une première étape 101 de fabrication d'un lingot en alliage haute entropie. Pour ce faire, on mélange les éléments sous forme pure ou en préalliage, puis ils sont fusionnés et l'ensemble est coulé pour former un lingot.This method comprises a first step 101 of manufacturing a high entropy alloy ingot. To do this, the elements are mixed in pure form or as a pre-alloy, then they are fused and the whole is cast to form an ingot.

Le procédé comporte ensuite une étape 102 de forgeage à chaud du lingot.The method then comprises a step 102 of hot forging of the ingot.

Le procédé comporte ensuite une étape 103 de laminage à chaud.The method then comprises a step 103 of hot rolling.

Le procédé comporte ensuite une étape 104 de laminage à froid.The method then comprises a step 104 of cold rolling.

Le procédé comporte ensuite une étape 105 de tréfilage.The method then comprises a step 105 of wire drawing.

Le procédé comporte ensuite une étape 106 de laminage à froid.The method then comprises a step 106 of cold rolling.

Naturellement l'invention n'est pas limitée aux modes de réalisation décrits en référence aux figures et des variantes pourraient être envisagées sans sortir du cadre de l'invention.Of course, the invention is not limited to the embodiments described with reference to the figures and variants could be envisaged without departing from the scope of the invention.

Ainsi, dans les exemples précédents, l'alliage Fe80-xMnxCo10Cr10 a été utilisé. Toutefois, d'autres alliages haute entropie pourraient être utilisés, comme par exemple :

  • Fe20Mn20Ni20Co20Cr20,
  • Fe40Mn27Ni26Co5Cr2,
  • Ta20Nb20Hf20Zr20Ti20,
  • Al20Li20Mg10Sc20Ti30,
  • Cr18.2Fe18.2Co18.2Ni18.2Cu18.2Al9.0.
Thus, in the previous examples, the Fe 80-x Mn x Co 10 Cr 10 alloy was used. However, other high entropy alloys could be used, such as:
  • Fe 20 Mn 20 Ni 20 Co 20 Cr 20 ,
  • Fe 40 Mn 27 Ni 26 Co 5 Cr 2 ,
  • Ta 20 Nb 20 Hf 20 Zr 20 Ti 20 ,
  • Al 20 Li 20 Mg 10 Sc 20 Ti 30 ,
  • Cr 18.2 Fe 18.2 Co 18.2 Ni 18.2 Cu 18.2 Al 9.0 .

Claims (8)

  1. Timepiece component containing a high-entropy alloy, the high-entropy alloy formed of 4 to 6 elements forming a single solid solution, the high-entropy alloy having a concentration of each main alloying element comprised between 1 and 55 at.%, wherein the high-entropy alloy satisfies the following formula: Fe80-xMnxCo10Cr10, where x is comprised between 25 and 79 at.%, and preferably x is comprised between 25 and 45 at.%.
  2. Timepiece component according to the preceding claim, wherein the high-entropy alloy satisfies the following formula: FeaMnbCocCrd where a, b, c et d are comprised between 1 and 55 at.%.
  3. Timepiece component according to claim 1, wherein the high-entropy alloy satisfies the following formula: FeaMnbNieCocCrd where a, b, c, d and e are comprised between 1 and 55 at. %.
  4. Timepiece component containing a high-entropy alloy, the high-entropy alloy formed of 5 elements forming a single solid solution, the high entropy alloy having a concentration of each main alloying element comprised between 1 and 55 at. %, wherein the high-entropy alloy satisfies the following formula: TaaNbbHfcZrdCre where a, b, c, d and e are comprised between 1 and 55 at. %.
  5. Timepiece component containing a high-entropy alloy, the high-entropy alloy formed of 5 elements forming a single solid solution, the high entropy alloy having a concentration of each main alloying element comprised between 1 and 55 at. %, wherein the high-entropy alloy satisfies the following formula: AlaLibMgcScdTie where a, b, c, d and e are comprised between 1 and 55 at. %.
  6. Timepiece component containing a high-entropy alloy, the high-entropy alloy formed of 6 elements forming a single solid solution, the high entropy alloy having a concentration of each main alloying element comprised between 1 and 55 at. %, wherein the high-entropy alloy satisfies the following formula: AlaCobCrcCudFeeNif where a, b, c, d, e and f are comprised between 1 and 55 at.%.
  7. Timepiece component according to any of the preceding claims, wherein the high-entropy alloy contains one or more interstitial elements from among the following: C, N, B.
  8. Timepiece component according to any of the preceding claims, wherein the high-entropy alloy contains one or more structural hardening elements from among the following: Ti, Al, Be, Nb.
EP17745346.1A 2016-09-30 2017-07-28 Timepiece component having a high-entropy alloy Active EP3519900B1 (en)

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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

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EP3519900B1 true EP3519900B1 (en) 2021-05-05

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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
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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

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EP3301520A1 (en) 2018-04-04
US20200241475A1 (en) 2020-07-30
WO2018059795A1 (en) 2018-04-05
JP6892914B2 (en) 2021-06-23
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US20210263470A1 (en) 2021-08-26
CN109804321B (en) 2021-07-27
CN109804321A (en) 2019-05-24

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