EP3695920B1 - Robuster ingot für die herstellung von bauteilen aus metallischen massivgläsern - Google Patents

Robuster ingot für die herstellung von bauteilen aus metallischen massivgläsern Download PDF

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Publication number
EP3695920B1
EP3695920B1 EP19156906.0A EP19156906A EP3695920B1 EP 3695920 B1 EP3695920 B1 EP 3695920B1 EP 19156906 A EP19156906 A EP 19156906A EP 3695920 B1 EP3695920 B1 EP 3695920B1
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EP
European Patent Office
Prior art keywords
ingot
melt
casting
glass
alloy
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EP19156906.0A
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German (de)
English (en)
French (fr)
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EP3695920A1 (de
Inventor
Tim GLÄSER
Hamed SHAKUR SHAHABI
Eugen Milke
Hans-Jürgen Wachter
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Heraeus Deutschland GmbH and Co KG
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Heraeus Deutschland GmbH and Co KG
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Priority to EP19156906.0A priority Critical patent/EP3695920B1/de
Priority to PCT/EP2020/052232 priority patent/WO2020164916A1/de
Priority to CN202080011844.XA priority patent/CN113382815B/zh
Priority to US17/427,597 priority patent/US20220118511A1/en
Priority to TW109103520A priority patent/TWI791947B/zh
Publication of EP3695920A1 publication Critical patent/EP3695920A1/de
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    • 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
    • B22D25/06—Special casting characterised by the nature of the product by its physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • 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
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00—Casting ingots, e.g. from ferrous metals
    • B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
    • 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
    • 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
    • C22C1/023—Alloys based on nickel
    • 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
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C16/00—Alloys based on zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/04—Amorphous alloys with nickel or cobalt as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/10—Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent

Definitions

  • the invention relates to a method for producing mechanically and thermally stable ingots (also called preforms) from alloys that can form a metallic solid glass. Furthermore, the invention relates to an ingot of a solid glass-forming alloy that is produced using the method according to the invention and the use of this ingot in a casting method.
  • BMG bulk metallic glasses
  • a metallic solid glass is to be understood as meaning a material with a critical casting thickness of at least one millimeter.
  • the existing systems include, among other things, precious metal-based alloys such as gold, platinum and palladium-based metallic bulk glasses, early transition metal-based alloys such as titanium or zirconium-based metallic bulk glasses, late transition metal-based systems, e.g. based on Copper, nickel or iron, but also systems based on rare earth metals, e.g. neodymium or terbium.
  • Components made of metallic solid glass can be produced using casting processes, since the necessary cooling rates for amorphous solidification can be achieved with these processes.
  • amorphous components In order to obtain amorphous components from a metallic bulk glass, it is usually necessary to quickly transfer the melt of a bulk glass-forming alloy into a mold. This filling of the mold with the melt preferably takes place by injection (injection molding) or sucking in (suction molding). In this way, the high cooling rates can be achieved and three-dimensional components made of metallic solid glass can be manufactured. Small manufacturing tolerances can be achieved by using casting processes such as injection molding.
  • Ingots of the alloy to be processed are necessary for casting processes, which serve as a supply of material to be processed and can be melted homogeneously. To do this, the ingots must have a sufficient volume so that enough material is available for the entire cast component and the additional spaces in the mold (the sprue ) can also be filled. Therefore, ingots that are as large as possible are desirable.
  • a homogeneous bulk glass-forming alloy is first produced. To do this, the individual components are mixed together and heated above the melting point, resulting in a homogeneous alloy. The individual components can be melted, for example, in an arc or by means of inductive heating. the The homogeneous alloy is then poured into molds and cooled to form an ingot. Generally, these ingots are in the form of cylindrical rods. In order for the ingots to contain enough material to completely fill the mold for a casting process for a three-dimensional component, the ingots must be sufficiently dimensioned. Typical diameters of cylindrical ingots made of bulk glass-forming alloys are in the range of about 20 mm. The length of an ingot is preferably at least 3 cm.
  • An object of the present invention was to provide an ingot made from a solid glass-forming alloy with a high critical casting thickness, which does not shatter during the production process and can be heated up more quickly during further thermal processing, such as injection molding.
  • the object of the invention was to provide a method for producing an ingot from a solid glass-forming alloy with a high critical casting thickness that does not shatter during the production process.
  • Another object of the invention was to provide ingots made of bulk glass-forming alloys that can be heated faster than conventional ingots.
  • the composition of the solid glass-forming alloy is not further restricted.
  • a solid glass-forming alloy is preferably to be understood as meaning an alloy with a critical casting thickness of at least one millimeter. This means that such an alloy can solidify amorphously up to a thickness of one millimeter at a suitable cooling rate.
  • alloys that can form metallic bulk glasses are selected from the group consisting of Ni-Nb-Sn, Co-Fe-Ta-B, Ca-Mg-Ag-Cu, C-oFe-B-Si -Nb, Fe-Ga-(Cr,Mo)(P,C,B), Ti-Ni-Cu-Sn, Fe-Co-Ln-B, Co-(Al,Ga)-(P,B,Si ), Fe-B-Si-Nb and Ni-(Nb,Ta)-Zr-Ti.
  • the metallic bulk glass can be a Zr-Cu-Al-Nb alloy.
  • this Zr-Cu-Al-Nb alloy preferably also has 23.5-24.5% by weight copper, 3.5-4.0% by weight aluminum and 1.5-2.0% by weight On niobium, the proportions by weight adding up to 100% by weight.
  • the latter alloy is commercially available under the name AMZ4® from Heraeus Kunststoff GmbH.
  • the alloy forming solid glass can contain or consist of the elements zirconium, titanium, copper, nickel and aluminum.
  • Particularly stable ingots can be produced from alloys of this composition that form solid glass.
  • a particularly well suited alloy for the production of stable inogts has the composition Zr 52.5 Ti 5 Cu 17.9 Ni 14.6 Al 10 , the indices indicating mol % of the respective elements in the alloy.
  • the alloy that forms solid glass preferably has a critical casting thickness of at least 5 mm, in particular at least 7 mm and entirely particularly preferably of at least 10 mm.
  • the maximum casting thickness is a measure of how easy or difficult it is for a metallic alloy to bring it into the glass state.
  • the alloy to be measured is processed in an electric arc to form a homogeneous melt and then poured into a water-cooled copper mold (also called permanent mold).
  • the mass of the copper mold is preferably at least a factor of 7 greater than the mass of the melt of the alloy to be determined.
  • the temperature of the homogeneous melt before casting is preferably at least 200° C., in particular 300° C. and very particularly preferably at least 400° C. above the melting temperature.
  • the temperature of the copper mold is 20°C.
  • cylindrical molded parts are cast with increasing diameters at a distance of 1 mm (e.g. 2mm, 3mm, 4mm, 5mm, 6mm, etc.).
  • the cylindrical molded parts produced are examined for their crystalline content using differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the cylinder diameter that is one millimeter smaller than the cylinder diameter at which the formation of a crystalline phase is first measured by DSC is given as the critical casting thickness.
  • DSC method 2) as described herein was used to determine the presence of a crystalline phase.
  • a homogeneous melt of a bulk glass-forming alloy is provided.
  • the homogeneous melt is preferably prepared by melting the individual elements of the alloy together.
  • the individual elements are preferably melted in an arc or by means of inductive heating.
  • the temperature of the homogeneous melt is preferably at least 200° C., in particular at least 300° C., and very particularly preferably at least 400° C., above the melting temperature of the respective solid glass-forming alloy.
  • the temperature of the melt, measured in degrees Celsius is at least 20%, in particular at least 50%, above the melting temperature of the alloy, since particularly stable ingots can be produced as a result.
  • the homogeneous melt is poured into a casting mold.
  • the shape of the mold is not further restricted.
  • the mold is preferably cylindrical.
  • the volume of the casting mold to be filled preferably has dimensions which are greater in all three spatial directions than the critical casting thickness of the alloy forming solid glass.
  • the material of the mold can preferably be selected from steel, titanium, copper, ceramic or graphite.
  • the mold preferably has a device with which the mold can be actively heated and/or cooled. In one embodiment of the invention, the mold can be actively heated, eg by electrical heating.
  • the ratio between the weight of the mold and the weight of the melt is preferably in the range of 7:1 or more, more preferably in the range of 10:1 or more.
  • the casting mold can be coated in the area that comes into contact with the melt.
  • the material of this coating of the mold is preferably selected from the group consisting of boron nitride, aluminum oxide (eg Al 2 O 3 ) and yttrium oxide (eg Y 2 O 3 ).
  • the coating preferably has or consists of a powder.
  • the thickness of the coating, in particular the powder coating can be in the range of 10-50 ⁇ m in one embodiment.
  • a layer of powder can have an advantageous effect on the mechanical properties of the ingot to be produced.
  • the coating can serve, among other things, to make it easier to remove the ingot from the mold.
  • the casting mold does not cool below the glass formation temperature of the solid glass-forming alloy at the contact surface with the melt for at least 5 seconds, in particular for at least 10 seconds and very particularly preferably for at least 30 seconds.
  • a melt is also referred to after the liquid melt has been transferred to the casting mold, even if the solidification process has already started and the solid glass-forming alloy is partially or completely solid, as long as the glass transition temperature has not yet been fallen below.
  • the casting mold does not cool below the glass formation temperature of the solid glass-forming alloy at any point on the contact surface with the melt for the specified period.
  • the determination of the glass formation temperature of the alloy is described under "Methods".
  • the temperature of the mold at the contact surface with the melt for the aforementioned period is at least 10° C., in particular at least 20° C. and particularly preferably at least 40° C. or at least 80° C. above the glass formation temperature of the solid glass-forming Alloy.
  • a temperature measuring probe can be embedded in the mold in such a way that it reaches the contact surface of the mold with the melt and measures there.
  • the temperature is preferably measured at half the length of the longest dimension of the ingot.
  • the temperature of the mold before filling with the melt is preferably adjusted so that the temperature of the mold after casting at the contact surface with the melt for at least 5 seconds, in particular for at least 10 seconds and most preferably for at least 30 seconds after contact with the mold does not fall below the glass formation temperature of the alloy.
  • the mold is preferably heated prior to contact with the melt.
  • the preferably set temperature of the mold directly before pouring the melt is at least 250°C, in particular at least 400°C and particularly preferably at least 500°C.
  • the casting mold can be heated in an oven, for example.
  • the mold can be actively heated, e.g. by electrical heating.
  • no additional pressure substantially above standard atmospheric pressure is applied to the melt after the melt has been poured.
  • “significantly above standard atmospheric pressure” can be understood to mean an overpressure of 1 bar or more.
  • an ingot can be produced from a bulk glass-forming alloy which does not shatter during the production process. Furthermore, the method can produce an ingot that does not shatter when heated to the melting temperature of the alloy within 50 seconds or less. In particular, an ingot which does not shatter when dropped three times from a height of 30 cm onto a flat, horizontal steel surface can be produced. In particular, the method can be used to produce an ingot that does not have an amorphous layer on the surface. The absence of an amorphous layer can be determined with a light microscope.
  • the invention relates to an ingot of a solid glass-forming alloy, the alloy having a critical casting thickness of at least 5 mm, and the ingot having an extent in all three spatial directions which is greater than the critical casting thickness, characterized in that that the ingot has a crystalline proportion of at least 90% by weight, in particular at least 95% by weight and particularly preferably at least 98% by weight, measured by DSC.
  • the critical casting thickness of the alloy is preferably at least 7 mm and in particular at least 10 mm.
  • the ingot according to the invention can be produced using the method described herein will.
  • the ingot according to the invention has no amorphous layer on the surface.
  • the term "no amorphous layer" can be understood as a layer which is no thicker than 200 ⁇ m, in particular no thicker than 100 ⁇ m and very particularly preferably no thicker than 50 ⁇ m.
  • the absence of an amorphous layer can preferably lead to the reduction of internal stresses in the ingot.
  • the absence of an amorphous layer on the surface of the ingot can be determined by optical microscopy (reflected light microscope).
  • a cross-section of the ingot is created using a diamond saw.
  • the cross-section is also called a metallurgical micrograph or cross-section.
  • the absence of amorphous portions can be determined by the absence of a phase transition visible to the naked eye under the light microscope. Phase transitions can be identified in the light microscope as transitions of different colors or different contrasts.
  • illustration 1 shows a micrograph of a cross section through an ingot that has amorphous areas. These amorphous areas can be seen as a bright area towards the edge (arrow 1). The inner area of the examined ingot shows no bright areas (arrow 2).
  • Figure 2 a micrograph of a cross-section through an ingot that does not have any amorphous areas. This can be recognized by the uniform material appearance without light spots.
  • Figure 3 shows a metallurgical micrograph of the sample Figure 2 at higher magnification. The polycrystalline structures and their grain boundaries can be clearly seen there. Furthermore, it can be seen that the crystalline structure of the ingot according to the invention extends to the edge, which confirms the absence of an amorphous phase (eg in the circled area). If an amorphous phase were to occur, it would preferably form at the edge first, as this is where the cooling rates can potentially be highest.
  • an amorphous phase eg in the circled area
  • the total volume of the amorphous layer on the ingot can be 5% or less, in particular 3% or less.
  • the crystallinity of the ingot can be measured using Differential Scanning Calorimetry (DSC).
  • the ingot is preferably solid and has no cavities, such as air inclusions.
  • the shape of the ingot is not limited.
  • the ingot may have a cylindrical shape.
  • the cylinder diameter preferably has a value of at least 5 mm, in particular at least 15 mm and very particularly preferably at least 25 mm, in each case with the condition that the diameter is greater than the critical casting thickness of the solid glass-forming alloy.
  • the length of the cylinder is preferably at least 3 cm.
  • the invention relates to a method for producing three-dimensional components from metallic solid glasses by means of casting methods, in particular injection molding, using the ingot according to the invention of a solid glass-forming alloy.
  • the ingot according to the invention is melted to form a homogeneous melt (30).
  • the complete melting of the ingot (20) preferably takes no longer than 60 seconds, in particular no longer than 40 seconds and very particularly preferably no longer than 20 seconds, it being possible for the ingot to be heated without cracking.
  • the heating-up time for already known ingots of the same dimensions is typically in the range of 80 seconds.
  • the homogeneous melt (30) is poured, in particular injected, into the mold for a three-dimensional component (40).
  • the casting mold for producing the three-dimensional component by means of the casting process is preferably dimensioned in such a way that it does not exceed the critical casting thickness of the alloy used at any point, since completely amorphous, three-dimensional components can be produced in this way.
  • the ingot can be used to produce three-dimensional components that can be produced with a high throughput in an injection molding machine.
  • the XRD measurements are carried out in accordance with DIN EN 13925-1:2003-07 and DIN EN 13925-2:2003-07.
  • a cross section of the material to be examined is prepared with a diamond saw.
  • the flat surface of the cross section is in the range of approx. 1 cm 2 .
  • the general measurement details used are summarized as follows: Diffraction: Bragg-Brentano; Detector: Scintillation Counter; Radiation: Cu K ⁇ 1.5406 ⁇ ; Source: 40kV, 25mA; Measurement method: reflection.
  • the empty sample holder is measured first to determine the background signal. This background measurement is subtracted from all subsequent measurements of the samples to be examined.
  • Discrete diffraction signals in the diffractogram can be evaluated according to the Debye-Scherrer method using the Bragg equation. When visible from discrete, crystalline peaks above the statistical noise, a crystalline proportion of at least 5% by weight is assumed. If no sharp diffraction signals can be determined in the diffractogram, the crystalline proportion is below 5%.
  • the DSC measurements within the scope of the invention are carried out in accordance with DIN EN ISO 11357-1:2017-02 and DIN EN ISO 11357-3:2018-07.
  • the sample to be measured in the form of a thin disc or foil (approx. 80 - 100 mg) is placed in the measuring device (NETZSCH DSC 404F1, NETZSCH GmbH, Germany).
  • the heating rate is 20.0 K/min.
  • Al 2 O 3 is used as the crucible material.
  • the heat flow is measured against an empty reference crucible, so that only the thermal behavior of the sample is measured.
  • Samples expected to be predominantly crystalline with little amorphous phase are measured according to the measurement method given above.
  • the complete crystallinity of the sample after undergoing the measurement procedure can be additionally confirmed by XRD, by the absence of broad, unspecific signals in the diffraction pattern that would indicate an amorphous phase.
  • the amorphous content of samples with more than 5% by weight can be determined by comparing the crystallization enthalpy of the unknown sample with the value for the completely amorphous sample from DSC method 2) (see below).
  • a sample of each of the cast cylinders is measured using DSC. As long as the diameter of the cylinder is below the critical casting thickness, the sample is completely amorphous before the start of the measurement and crystallizes during the DSC measurement in step a) of the measurement method.
  • the crystallization enthalpy of the alloy is determined from the measurement of the completely amorphous material. The crystallization enthalpy is determined for all samples with increasing cylinder diameter. The crystallization enthalpy determined for samples whose cylinder diameter is below the critical casting thickness is constant within the measurement inaccuracy.
  • the critical casting thickness is determined as the cylinder diameter up to which the crystallization enthalpy is constant with increasing diameter.
  • step a) the crystallization of the amorphous sample takes place.
  • step c) the thermal behavior of the already fully crystallized sample is recorded.
  • the measurement from step c) is subtracted from the measurement from step a).
  • the resulting curve includes an endothermic transition at lower temperature and an exothermic peak at higher temperature.
  • the signal at higher temperature corresponds to the crystallization process.
  • the endothermic signal corresponds to the glass transition.
  • a line tangent to the baseline is determined (by linear fitting) in front of the glass transition region.
  • a second tangent is determined at the inflection point (corresponding to the peak time value of the first derivative) of the glass transition region.
  • the temperature value at the intersection of the two tangents indicates the glass transition temperature (T f according to AST; 1356-03).
  • the individual components were melted under protective gas by means of inductive melting into a homogeneous alloy with the composition Zr 52.5 Ti 5 Cu 17.9 Ni 14.6 Al 10 .
  • This alloy has a glass transition temperature of 403 °C.
  • 80 g of the homogeneous alloy were brought to a temperature above the melting point of the alloy (805° C.) by means of inductive heating in a crucible.
  • Table 1 shows the temperatures of the respective melt for the respective test.
  • the mold was preheated in an oven to a temperature defined in Table 1.
  • the respective homogeneous melt according to Table 1 was then poured into a casting mold.
  • the mold had a cylindrical shape with an inner diameter of 19 mm. The temperature of the melt was continuously measured after filling the cylindrical mold.
  • the measured values for the temperature of the melt after 10 seconds in the mold can be read in Table 1.
  • Table 1 Table 1 ⁇ /b> example 1 2 3 4 5 T melt [°C] 1050 1100 1200 1250 1350 T mold [°C] 50 50 250 400 600 mold copper stolen stolen stolen stolen weight ratio 1:17 1:15 1:9 1:15 1:15 coating d.
  • Examples 1 and 2 in Table 1 are comparative examples, Examples 3-5 are examples according to the invention.
  • the quality of the cast ingots was assessed according to the following criteria: Poor-quality cast parts already shatter while cooling in the mold. Good quality cast ingots will remain intact if heated to melting temperature within 50 seconds or less at a power of 5 kW. Very good quality ingots also withstand a drop test from a height of 30 cm onto a flat steel plate three times in a row without shattering. It is clear from Examples 1-5 that ingots in which the temperature of the melt was above the glass transition temperature after 10 seconds were significantly more robust than ingots in which the temperature of the melt was below.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Continuous Casting (AREA)
EP19156906.0A 2019-02-13 2019-02-13 Robuster ingot für die herstellung von bauteilen aus metallischen massivgläsern Active EP3695920B1 (de)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP19156906.0A EP3695920B1 (de) 2019-02-13 2019-02-13 Robuster ingot für die herstellung von bauteilen aus metallischen massivgläsern
PCT/EP2020/052232 WO2020164916A1 (de) 2019-02-13 2020-01-30 Robuster ingot für die herstellung von bauteilen aus metallischen massivgläsern
CN202080011844.XA CN113382815B (zh) 2019-02-13 2020-01-30 用于生产由块体金属玻璃制成的组件的稳定铸锭
US17/427,597 US20220118511A1 (en) 2019-02-13 2020-01-30 Robust ingot for the production of components made of metallic solid glasses
TW109103520A TWI791947B (zh) 2019-02-13 2020-02-05 用於製造由塊狀金屬玻璃製成的組件的強化錠

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EP19156906.0A EP3695920B1 (de) 2019-02-13 2019-02-13 Robuster ingot für die herstellung von bauteilen aus metallischen massivgläsern

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EP3695920A1 EP3695920A1 (de) 2020-08-19
EP3695920B1 true EP3695920B1 (de) 2022-04-06

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CN104213054B (zh) * 2014-09-03 2017-02-15 中国科学院金属研究所 液相分离双相块体金属玻璃材料及其制备方法
US20160067766A1 (en) * 2014-09-08 2016-03-10 Apple Inc. 3d printed investment molds for casting of amorphous alloys and method of using same
JP6334626B2 (ja) * 2016-09-01 2018-05-30 アップル インコーポレイテッド アモルファス合金インゴットの金型不要の連続的製造

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TWI791947B (zh) 2023-02-11
WO2020164916A1 (de) 2020-08-20
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CN113382815A (zh) 2021-09-10
EP3695920A1 (de) 2020-08-19
TW202035718A (zh) 2020-10-01

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