EP3170579A1 - Verfahren zur herstellung eines teils aus amorphem metall - Google Patents

Verfahren zur herstellung eines teils aus amorphem metall Download PDF

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Publication number
EP3170579A1
EP3170579A1 EP15195197.7A EP15195197A EP3170579A1 EP 3170579 A1 EP3170579 A1 EP 3170579A1 EP 15195197 A EP15195197 A EP 15195197A EP 3170579 A1 EP3170579 A1 EP 3170579A1
Authority
EP
European Patent Office
Prior art keywords
mold
manufacturing
component
partially amorphous
amorphous
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.)
Withdrawn
Application number
EP15195197.7A
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English (en)
French (fr)
Inventor
Tommy Carozzani
Yves Winkler
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 EP15195197.7A priority Critical patent/EP3170579A1/de
Priority to US15/776,861 priority patent/US10981223B2/en
Priority to JP2018525451A priority patent/JP2019501780A/ja
Priority to CN202310723816.6A priority patent/CN116809900A/zh
Priority to PCT/EP2016/074369 priority patent/WO2017084807A1/fr
Priority to RU2018121843A priority patent/RU2018121843A/ru
Priority to EP16781383.1A priority patent/EP3377247B1/de
Priority to CN201680067371.9A priority patent/CN108290213A/zh
Publication of EP3170579A1 publication Critical patent/EP3170579A1/de
Priority to HK18116387.7A priority patent/HK1257133A1/zh
Priority to JP2021012946A priority patent/JP2021079451A/ja
Priority to JP2022169031A priority patent/JP2023012487A/ja
Priority to JP2024061544A priority patent/JP2024091628A/ja
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C9/00—Moulds or cores; Moulding processes
    • B22C9/02—Sand moulds or like moulds for shaped castings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D13/00—Centrifugal casting; Casting by using centrifugal force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D15/00—Casting using a mould or core of which a part significant to the process is of high thermal conductivity, e.g. chill casting; Moulds or accessories specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D25/00—Special casting characterised by the nature of the product
    • B22D25/02—Special casting characterised by the nature of the product by its peculiarity of shape; of works of art
    • B22D25/026—Casting jewelry articles
    • 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
    • G04B17/00—Mechanisms for stabilising frequency
    • G04B17/20—Compensation of mechanisms for stabilising frequency
    • G04B17/22—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature
    • G04B17/227—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature composition and manufacture of the material used
    • 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
    • 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
    • G04B15/00—Escapements
    • G04B15/14—Component parts or constructional details, e.g. construction of the lever or the escape wheel
    • 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
    • G04B17/00—Mechanisms for stabilising frequency
    • G04B17/20—Compensation of mechanisms for stabilising frequency
    • G04B17/28—Compensation of mechanisms for stabilising frequency for the effect of imbalance of the weights, e.g. tourbillon
    • G04B17/285—Tourbillons or carrousels
    • 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

Definitions

  • the present invention relates to a method for manufacturing a micromechanical piece of amorphous metal.
  • the technical field of the invention is the technical field of fine mechanics. More specifically, the invention will belong to the technical field of manufacturing methods of amorphous metal parts.
  • micromechanical parts Various methods are known for producing micromechanical parts. Indeed, these can be performed by micro-machining or stamping or by injection into a mold.
  • an advantageous solution consists in directly casting the piece of amorphous metal so as to obtain by foundry the final geometry or a geometry close to the final geometry requiring little retouching.
  • the absence of crystalline structure implies that the properties of the amorphous metal part (in particular the mechanical properties, the hardness and the polishability) do not depend on the method of manufacture. This is a major advantage over traditional polycrystalline metals where the castings have lower properties compared to forged parts.
  • a first problem comes from the cooling of the mold. This disadvantage can be seen in two aspects.
  • a first aspect is that the cooling must not be too slow because there is then a risk of partial or total crystallization and thus lose the properties of the amorphous metals.
  • the cooling must not be too slow because there is then a risk of partial or total crystallization and thus lose the properties of the amorphous metals.
  • the presence of a single crystallite may be unacceptable for reasons of mechanical properties or visual appearance, since such crystallites will inevitably occur during the finishing steps. It is therefore essential to have a sufficiently rapid cooling during casting to ensure the amorphicity of the room.
  • the molds are made of metal, for example steel or copper, for quickly extracting heat. Depending on the capacity of the chosen alloy to become amorphous, it is possible with this method to obtain pieces of thickness of the order of 10mm.
  • the second aspect to consider is that the cooling must not be too fast because there is a risk of solidification before the mold cavity is completely filled.
  • metal molds such as copper or steel
  • the thermal energy is quickly dispersed causing a risk of early solidification.
  • a second disadvantage is a formatting problem. This formatting problem comes from the small size of the mold and the footprint of the micromechanical part to be manufactured. For some geometries, in particular recessed geometries, indémoulables, it may be necessary to add inserts in the mold to be eliminated after shaping, and lost. For complex shapes, the cost of these inserts and additional operations related thereto can become very high, making the process unusable industrially.
  • the amorphous metals have the particular characteristic of softening while remaining amorphous in a given temperature range [Tg - Tx] specific to each alloy and low because these temperatures Tg and Tx are low. This makes it possible to accurately reproduce fine and precise geometries because the viscosity of the alloy decreases sharply and the latter can be easily deformed in order to match all the details of a mold.
  • the time available before the alloy crystallizes is limited. If the geometry has many complexities of small thicknesses, the time required for complete filling of the mold may be longer than the time available, resulting in partial or complete crystallization of the part and a loss of its mechanical properties in particular.
  • LIGA A similar known technique is LIGA technology.
  • the LIGA consists of three main stages of treatment; lithography, electroplating and molding.
  • X-Ray LIGA is a microtechnology manufacturing process developed in the early 1980s.
  • an X-ray sensitive photoresist typically PMMA (poly (methylmethacrylate)
  • PMMA poly (methylmethacrylate)
  • Chemical removal from exposed (or unexposed) areas photoresist polymer provides a three-dimensional structure which can be filled by metal plating.
  • the resin is chemically removed to produce a metal mold insert.
  • the mold insert can be used to produce polymer or ceramic parts by injection molding.
  • the main advantage of the LIGA technique is the precision achieved by the use of X-ray lithography (DXRL). This technique allows for microstructures with high aspect ratios and high accuracy to be manufactured in a variety of materials (metals, plastics and ceramics).
  • the LIGA UV technique uses an inexpensive ultraviolet light source, such as a mercury lamp, to expose a photoresist, typically SU-8. Because heating and transmission are not a problem in optical masks, a simple chrome mask can be substituted for the sophisticated X-ray mask technique. These simplifications make the technique LIGA UV, a technique much cheaper and more accessible than his counterpart X-ray. However, the LIGA UV technique is not as efficient in producing precision molds and is therefore used when the cost has to be kept low and when very high aspect ratios are not needed.
  • the LIGA process poses a problem concerning the choice of materials. Indeed, two materials are needed: a material for the substrate and a material that will be deposited.
  • the material for the substrate must be photo-structuring so that the plaster or zircon is not usable.
  • For the deposited material it must be deposited electroplating so that the metal materials are the only ones that can be envisaged.
  • such materials generally have thermal characteristics such that they ensure good heat dissipation and therefore good cooling. This ability to dissipate heat energy would cause, for an amorphous metal alloy formed in the LIGA mold, a hardening too fast and thus prevent good formation of parts.
  • step c) consists of dissolving said mold.
  • said first material is subjected to a rise in temperature above its melting point allowing it to lose locally any crystalline structure, said rise being followed by cooling to a temperature below its temperature. transition glass allowing said first material to become at least partially amorphous.
  • the shaping step b) is simultaneous with a treatment rendering said first material at least partially amorphous, by subjecting it to a temperature above its melting point followed by cooling to a temperature lower than its glass transition temperature allowing it to become at least partially amorphous, during a casting operation.
  • This embodiment is characterized in that that the critical cooling rate of the first material is less than 10K / s.
  • the shaping is done by injection.
  • the shaping is done by centrifugal casting.
  • the second material is zircon having an effusivity of 2300 J / K / m 2 / s 0.5 .
  • the second material is of the plaster type composed mainly of gypsum and / or silica, having an effusivity of between 250 and 1000 J / K / m 2 / s 0.5 .
  • the first material has a critical cooling rate of less than or equal to 10 K / s.
  • the invention also relates to a component made in a first material being a metallic material capable of becoming at least partially amorphous, characterized in that it is manufactured using the method according to the invention.
  • the invention further relates to a timepiece or jewelery comprising the component according to the invention, said component is selected from the list comprising a middle part, a bezel, a bracelet link, a cog, a needle, a crown, an escapement anchor or balance, a tourbillon cage, a ring, a cufflink or an earring or a pendant.
  • the Figures 1 to 6 represent the various steps of the method of producing a watchmaking or jewelery component 1 also called first piece 1 according to the present invention.
  • This first piece 1 is made of a first material.
  • This first piece 1 may be a piece of clothing such as a caseband, a bezel, a bracelet link, a ring, cufflinks or earrings or a pendant or a functional piece such as a cogwheel 3, a needle , a crown, an anchor 5 or a balance 7 exhaust system 9, a tourbillon cage.
  • the first material is advantageously an at least partially amorphous material. More particularly, the material is metallic, it is understood that it comprises at least one metal or metalloid element in a proportion of at least 50% by weight.
  • the first material may be a homogeneous metal alloy or an at least partially or totally amorphous metal. The first material is thus chosen capable of locally losing any crystalline structure during a rise in temperature above its melting temperature followed by sufficiently rapid cooling to a temperature below its glass transition temperature, allowing it to become at least partially amorphous.
  • the metal element may be valuable or not.
  • the first step, represented at figure 2 is to provide a mold 10.
  • This mold 10 has a cavity 12 which is the negative of the part 1 to achieve.
  • This type of mold consists of a mold 10 made of a material that can be destroyed or dissolved after use to release said part.
  • the advantage of this type of mold is its ease of manufacture and demolding, which is independent of the geometry of the print. It is thus possible to easily make fingerprints of complex geometries and / or recesses, without inserts.
  • This mold may be obtained by covering a wax or resin model, itself obtained by injection, additive manufacturing, machining, or sculpture.
  • This mold 10 comprises a conduit 14 so that the liquid metal can be poured therein.
  • This mold 10 is thus made of a second material.
  • the mold material is chosen to have specific thermal properties.
  • the aim here is to have a mold for casting lost wax which is made of a material allowing the amorphous material of the micromechanical part not to crystallize while completely filling the mold cavity.
  • Crystallization of amorphous metals occurs when these, when in a viscous or liquid state, are not cooled fast enough to prevent the atoms from structuring themselves.
  • this characteristic is defined by the critical cooling rate, Rc, ie the minimum cooling rate to be respected between the melting point and the glass transition temperature in order to maintain an amorphous state of the material. Therefore, it becomes necessary to have a mold 10 made of a material that dissipates heat energy well enough to ensure a cooling rate R greater than Rc.
  • foundry molds are made of steel or cuprous alloys to have a high R value.
  • the present invention proposes to use the criterion of thermal effusivity E in combination with Rc.
  • the effusivity makes it possible, according to the thickness of the first part to be produced, to obtain a cooling which guarantees an amorphous state of the material, that is to say R> Rc. Indeed, if the criterion of effusiveness is important, the amorphicity is related to the thickness of the part to be manufactured. It is easily understood that, for a given thickness, a high effusivity may result in solidification of the material before it has been able to fill the entire mold while too weak effusivity may cause crystallization. According to the invention, it will be considered that the effusivity will be chosen within a range of 250 to 2500 J / K / m 2 / s 0.5 . As an example of material, the effusivity of plaster type materials is 250 - 1000 J / K / m 2 / s 0.5 while for zircon, it will be 2300 J / K / m 2 / s 0.5 .
  • the second step is to provide the first material, that is to say the material constituting the first part 1. Once provided with the material, the next step of this second step is to shape it as visible to the Figures 3 and 4 . For this, a casting process is used.
  • Such a method consists in taking the first material which was provided during the third step without having made it undergo a treatment rendering it at least partially amorphous and put it in liquid form. This liquid forming is done by melting said first material in a pouring container 20.
  • the first material in liquid form is poured into the cavity 2 of the mold.
  • the first material is then cooled so as to give it an amorphous shape.
  • the cooling is carried out by heat dissipation of the mold 10, that is to say by using the thermal characteristics of the constituent material of the mold.
  • the constituent material of the mold 10 will be chosen to have an effusivity in the range of 250 to 2500 J / K / m 2 / s 0.5 , this thermal effusivity of a material being the capacity of the latter to exchange thermal energy with its environment.
  • this thermal effusivity of a material being the capacity of the latter to exchange thermal energy with its environment.
  • the cooling rate R is low compared to the traditionally used metal molds.
  • the effusivity of the steel is more than 10'000 J / K / m 2 / s 0.5 and copper more than 35'000 J / K / m 2 / s 0.5 .
  • This critical cooling rate Rc will be less than 15 K / s.
  • a first piece of amorphous metal having a thickness of between 0.5 mm and 1.4 mm, being understood as explained above that details of smaller thickness are feasible if they are punctual and limited in size. Similarly, parts or parts of parts greater than 1.4 mm in thickness can be made without crystallization if they are considered as point and small details.
  • An advantage of casting a metal or alloy capable of being amorphous is to have a low melting point. Indeed, the melting temperatures of metals or alloys capable of having an amorphous form, are in general two to three times lower than those of conventional alloys when one considers compositions of the same types. For example, the melting temperature of Zr41.2Ti13.8Cu12.5Ni10Be22.5 alloy is 750 ° C compared to 1500-1700 ° C of zirconium Zr and Ti titanium alloys. This avoids damaging the mold.
  • Another advantage is that the solidification shrinkage, for an amorphous metal, is very low, less than 1% relative to the shrinkage of 5 to 7% for a crystalline metal. This advantage allows to use the principle of casting without fear of surface defects or significant changes in size that would be the consequence of said withdrawal.
  • Another advantage is that the mechanical and polishability properties of the amorphous metals do not depend on the process of as long as they are amorphous.
  • the parts obtained by casting will have the same properties as forged parts, machined, or deformed hot, which is a major advantage over crystalline metals whose properties strongly depend on the crystal structure, itself related to the history of the process of obtaining the piece.
  • the casting may be of the gravitational type.
  • the metal fills the mold under the effect of gravity.
  • the casting may be of the centrifugal type.
  • centrifugal casting utilizes the principle that the mold is rotated rapidly. The liquid metal poured inside sticks to the wall by centrifugal force and solidifies. This technique allows a centrifugation and a pressure on the material which causes a degassing and expels to the external part the impurities contained in the bath of liquid metal. Smaller cavities can be filled compared to simple gravitational casting.
  • the casting may be of the injection type.
  • injection molding uses the principle that the mold is filled with a piston that applies a very large force to push the liquid metal. This thrust then makes it possible to introduce the liquid metal into the mold in order to better fill it.
  • the casting may be of the counter-gravity type, by die casting, by vacuum casting.
  • the third step represented at figure 5 consists in separating the first piece 1 from the mold 10.
  • the mold 10 in which the amorphous metal has been overmolded to form the first part 1, is destroyed using a jet of water under high pressure, by dissolved in water or chemical solution, or by mechanical removal.
  • a chemical solution it is chosen to specifically attack the mold 10.
  • the purpose of this step is to dissolve the negative 1 without dissolving the first piece 5 made of amorphous metal.
  • a solution of hydrofluoric acid is used to dissolve the mold. The final result is then obtaining the first piece of amorphous metal.
  • the first step consisting in acquiring the negative 1 can also include the fact of preparing the negative. Indeed, it is possible to decorate the negative 1 so that surface states can be directly made on the first part. . These surface conditions can be a decoration "Geneva coast", beaded, snailed diamond or satin.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Molds, Cores, And Manufacturing Methods Thereof (AREA)
  • Adornments (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
EP15195197.7A 2015-11-18 2015-11-18 Verfahren zur herstellung eines teils aus amorphem metall Withdrawn EP3170579A1 (de)

Priority Applications (12)

Application Number Priority Date Filing Date Title
EP15195197.7A EP3170579A1 (de) 2015-11-18 2015-11-18 Verfahren zur herstellung eines teils aus amorphem metall
RU2018121843A RU2018121843A (ru) 2015-11-18 2016-10-11 Способ производства детали из аморфного металла
JP2018525451A JP2019501780A (ja) 2015-11-18 2016-10-11 アモルファス金属部品の製造方法
CN202310723816.6A CN116809900A (zh) 2015-11-18 2016-10-11 制造无定形金属零件的方法
PCT/EP2016/074369 WO2017084807A1 (fr) 2015-11-18 2016-10-11 Procede de fabrication d'une piece en metal amorphe
US15/776,861 US10981223B2 (en) 2015-11-18 2016-10-11 Method for manufacturing an amorphous metal part
EP16781383.1A EP3377247B1 (de) 2015-11-18 2016-10-11 Verfahren zur herstellung eines teils aus amorphem metall
CN201680067371.9A CN108290213A (zh) 2015-11-18 2016-10-11 制造无定形金属零件的方法
HK18116387.7A HK1257133A1 (zh) 2015-11-18 2018-12-21 製造無定形金屬零件的方法
JP2021012946A JP2021079451A (ja) 2015-11-18 2021-01-29 アモルファス金属部品の製造方法
JP2022169031A JP2023012487A (ja) 2015-11-18 2022-10-21 アモルファス金属部品の製造方法
JP2024061544A JP2024091628A (ja) 2015-11-18 2024-04-05 アモルファス金属部品の製造方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP15195197.7A EP3170579A1 (de) 2015-11-18 2015-11-18 Verfahren zur herstellung eines teils aus amorphem metall

Publications (1)

Publication Number Publication Date
EP3170579A1 true EP3170579A1 (de) 2017-05-24

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP15195197.7A Withdrawn EP3170579A1 (de) 2015-11-18 2015-11-18 Verfahren zur herstellung eines teils aus amorphem metall
EP16781383.1A Active EP3377247B1 (de) 2015-11-18 2016-10-11 Verfahren zur herstellung eines teils aus amorphem metall

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP16781383.1A Active EP3377247B1 (de) 2015-11-18 2016-10-11 Verfahren zur herstellung eines teils aus amorphem metall

Country Status (7)

Country Link
US (1) US10981223B2 (de)
EP (2) EP3170579A1 (de)
JP (4) JP2019501780A (de)
CN (2) CN108290213A (de)
HK (1) HK1257133A1 (de)
RU (1) RU2018121843A (de)
WO (1) WO2017084807A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3502787A1 (de) * 2017-12-22 2019-06-26 The Swatch Group Research and Development Ltd Herstellungsverfahren einer unruh für uhren
CH716669A1 (fr) * 2019-10-03 2021-04-15 Richemont Int Sa Procédé de fabrication d'un arbre de pivotement de balancier.
CN113351846A (zh) * 2021-06-15 2021-09-07 松山湖材料实验室 一种谐波减速器用非晶柔轮的制备方法

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EP3839624B1 (de) * 2019-12-18 2023-09-13 Nivarox-FAR S.A. Verfahren zur herstellung einer uhrkomponente
EP4282557A1 (de) * 2022-05-25 2023-11-29 Patek Philippe SA Genève Gerät zur herstellung eines werkstücks aus amorphem metall und verfahren zur herstellung eines solchen werkstücks

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CN113351846A (zh) * 2021-06-15 2021-09-07 松山湖材料实验室 一种谐波减速器用非晶柔轮的制备方法
CN113351846B (zh) * 2021-06-15 2022-11-25 松山湖材料实验室 一种谐波减速器用非晶柔轮的制备方法

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RU2018121843A (ru) 2019-12-19
HK1257133A1 (zh) 2019-10-11
JP2021079451A (ja) 2021-05-27
EP3377247B1 (de) 2021-07-28
JP2024091628A (ja) 2024-07-04
WO2017084807A1 (fr) 2017-05-26
US10981223B2 (en) 2021-04-20
JP2019501780A (ja) 2019-01-24
CN108290213A (zh) 2018-07-17
JP2023012487A (ja) 2023-01-25
US20190262896A1 (en) 2019-08-29
CN116809900A (zh) 2023-09-29

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