Classifications

• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C30/00—Alloys containing less than 50% by weight of each constituent
  • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
  • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
  • B22D21/02—Casting exceedingly oxidisable non-ferrous metals, e.g. in inert atmosphere
  • B22D21/025—Casting heavy metals with high melting point, i.e. 1000 - 1600 degrees C, e.g. Co 1490 degrees C, Ni 1450 degrees C, Mn 1240 degrees C, Cu 1083 degrees C
• • 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
• • 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
  • C22C1/11—Making amorphous alloys
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C30/00—Alloys containing less than 50% by weight of each constituent
  • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C45/00—Amorphous alloys
  • C22C45/001—Amorphous alloys with Cu as the major constituent
• • C—CHEMISTRY; METALLURGY
  • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
  • C22C—ALLOYS
  • C22C9/00—Alloys based on copper

Definitions

• Metallic glasses also called amorphous metals
• amorphous metals have very high strengths. Furthermore, they show no or only a very small change in volume during solidification, so that the possibility of shaping close to final shape without freezing shrinkage opens up.
• metallic glasses with a dimension of at least 1 mm x 1 mm x 1 mm can be produced with an alloy, these glasses are also referred to as solid metallic glasses or metallic solid glass (English: “Bulk Metallic Glasses” (“ BMG ”)).
• metallic glasses especially metallic solid glasses, very interesting construction materials, which are in principle suitable for the production of components in mass production processes such as injection molding, without further processing steps would be mandatory erformlich after molding.
• a measure of the glass-forming ability of an alloy is therefore, for example, the maximum or "critical" diameter up to which a specimen cast from the melt essentially still has an amorphous structure. This is also called critical casting thickness.
• Metallic glasses can not only be formed by melt-metallurgical processes, but can also be shaped by thermoplastic molding at comparatively low temperatures, analogous to thermoplastics or silicate glasses. For this purpose, the metallic glass is first heated above the glass transition point and then behaves like a highly viscous liquid that can be reshaped at relatively low forces. Following deformation, the material is again cooled below the glass transition temperature.
• a metallic glass may, at least temporarily, be exposed to an elevated temperature, which may even be above the glass formation temperature T g .
• the thermoplastic molding also involves heating the metallic glass to a temperature above the gas formation temperature T g .
• the higher this ⁇ T x value the greater the "temperature window" for thermoplastic molding and the lower the risk of unwanted crystallization when the metallic glass is temporarily exposed to a temperature above T g .
• Improved melt-forming ability of an alloy upon cooling from the melt does not automatically result in improved heat resistance (ie, a higher ⁇ T x value) of the metallic glass made from this alloy.
• ⁇ T x value improved heat resistance
• These are usually independent parameters that may even behave in opposite directions.
• care must also be taken that this does not occur at the expense of the glass-forming ability on cooling from the melt.
• the alloys most commonly used today for the production of metallic glasses are Zr-based alloys.
• a disadvantage of these alloys is the rather high material price for zirconium.
• US 5,618,359 describes Zr and Cu based alloys for the production of metallic glasses.
• the alloys contain at least 4 alloying elements.
• One of the Cu-based alloys has the composition Cu 45 Ti 33.8 Zr 11.3 Ni 10 and can be cast to an amorphous specimen having a thickness of 4 mm.
• US 2006/0231169 A1 describes alloys for the production of metallic glasses, which may be Cu based, among others.
• the alloy produced in Example 3 has the composition Cu 47 Ti 33 Zr 7 Ni 8 Si 1 Nb 4 . Starting from the alloy Cu 47 Ti 34 Zr 11 Ni 8 , Ti was substituted by Si and Zr by Nb.
• the alloy prepared in Comparative Example 3 has the composition Cu 47 Ti 33 Zr 11 Ni 8 Si 1 .
• An object of the present invention is to provide an alloy having as high a ⁇ Tx value as possible (ie, a wide temperature window for thermoplastic molding), but not at the expense of glass forming capability, and which is inexpensive to produce.
• the improved thermal stability should not adversely affect other relevant properties such as hardness.
• alloys with the above-defined composition have high ⁇ T x values and thus improved heat resistance with a still good glass-forming capability.
• the alloys according to the invention are thus very well suited eg for thermoplastic molding.
• Si when present in the alloy, its concentration is at most 2 at% (e.g., 0.5 at% ⁇ Si ⁇ 2 at%), provided that the total concentration of Sn and Si is at most 4 at%.
• the values for a and b define the atomic ratio of Ti to Zr.
• the alloy according to the invention contains oxygen, it is present in a concentration of at most 1.7 at%, for example 0.01-1.7 at% or 0.02-1.0 at%.
• the proportion of unavoidable impurities in the alloy is preferably less than 0.5 at%, more preferably less than 0.1 at%, even more preferably less than 0.05 at% or even less than 0.01 at%.
• the composition of the alloy can be determined by inductively coupled plasma optical emission spectrometry (ICP-OEC).
• the glass transition temperature T g and the crystallization temperature T x are determined by DSC (Differential Scanning Calorimetry). In each case the onset temperature is used. The cooling and heating rates are 20 ° C / min. The DSC measurement is carried out under an argon atmosphere in an alumina crucible.
• the alloy is an amorphous alloy.
• the alloy of the invention has a crystallinity of less than 50%, more preferably less than 25%, or is even completely amorphous.
• a completely amorphous material shows no diffraction reflections in X-ray diffraction.
• the crystalline fraction is determined by DSC as a ratio of maximum crystallization enthalpy (determined by crystallization of a fully amorphous reference sample) and the actual enthalpy of crystallization in the sample.
• the invention further relates to a method for producing the alloy described above, wherein the alloy is obtained from a melt containing Cu, Ti, Zr, Ni, Sn and optionally Si.
• the melt is preferably kept under an inert gas atmosphere (e.g., a noble gas atmosphere).
• an inert gas atmosphere e.g., a noble gas atmosphere
• the constituents of the alloy may each be incorporated into the melt in their elemental form (e.g., elemental Cu, etc.). Alternatively, it is also possible that two or more of these metals are pre-alloyed in a starting alloy and then this starting alloy is introduced into the melt.
• the alloy By cooling and solidification of the melt, the alloy is obtained as a solid or solid.
• the melt can, for example, be poured into a mold or subjected to atomization.
• the alloy can be obtained in the form of a powder whose particles have a substantially spherical shape.
• Suitable atomization methods are known to the person skilled in the art, for example gas atomization (for example using nitrogen or a noble gas such as argon or helium as atomizing gas), plasma atomization, centrifugal atomization or atomized atomization (eg a "rotating electrode” process (REP). designated method, in particular a "Plasma Rotating Electrode” process (PREP)).
• EIGA Electrode Induction Melting Gas Atomization
• inductive melting of the starting material and then gas atomization.
• the powder obtained via the atomization can then be used in an additive manufacturing process or subjected to a thermoplastic molding.
• the present invention relates to a metallic solid glass containing or even consisting of the alloy described above.
• the metallic solid glass preferably has a dimension of at least 1 mm ⁇ 1 mm ⁇ 1 mm.
• the metallic solid glass has a crystallinity of less than 50%, more preferably less than 25%, or is even completely amorphous.
• the preparation of the metallic solid glass can be carried out by methods which are known to the person skilled in the art.
• the alloy described above is subjected to additive manufacturing or thermoplastic molding or cast as a melt into a mold.
• the alloy may be used in the form of a powder (for example, a powder obtained via atomization).
• Additive manufacturing refers to a process in which a component is built up layer by layer on the basis of digital 3D design data by depositing material. Usually, a thin layer of the powder is first applied to the build platform. Over a sufficiently high energy input, for example in the form of a laser or electron beam, the powder is at least partially melted at the locations that specify the computer-generated design data. Thereafter, the building platform is lowered and there is another powder application.
• a sufficiently high energy input for example in the form of a laser or electron beam
• the further powder layer is at least partially melted again and combines at the defined locations with the underlying layer. These steps are repeated until the component is in its final form.
• thermoplastic molding is usually carried out at a temperature which is between T g and T x of the alloy.
• Inventive alloys E1-E8 were prepared, the respective composition of which is given in Table 1 below. In the comparative examples, the production of the alloys CE1-CE5 was carried out.
• the ⁇ T x value (ie the distance between crystallization temperature T x and glass formation temperature T g ) and the critical casting thickness D c of the alloys are given in Table 1.
• the determination of the glass transition temperature T g and the crystallization temperature T x was carried out by DSC on the basis of the onset temperatures and with cooling and heating rates of 20 ° C / min.
• the alloys were produced in an electric arc furnace made of pure elements by melting and melting to form a compact body, which was melted again and poured into a Cu mold.
• Table 1 Composition of the alloys and their ⁇ T ⁇ sub> x ⁇ / sub> and D ⁇ c> values Cu [at%] Ti [at%] Zr [at%] Ni [at%] Sn [at%] Si [at%] ⁇ T x [° C] Dc [mm]
• the alloy of Comparative Example CE1 has the composition Cu 47 Ti 34 Zr 11 Ni 8 . If a small amount of copper is substituted by Sn, there is a significant increase in the ⁇ T x value and also the D c value increases very clearly, see Example E1. Even with a change in the relative proportions of Ti and Zr, this improvement in the ⁇ T x value compared to the starting alloy, see Examples E2 and E3.

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• Materials Engineering (AREA)
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• Organic Chemistry (AREA)
• Powder Metallurgy (AREA)
• Manufacture Of Metal Powder And Suspensions Thereof (AREA)

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• 2017
  • 2017-08-18 EP EP17186878.9A patent/EP3444370B1/fr active Active
• 2018
  • 2018-08-09 WO PCT/EP2018/071580 patent/WO2019034506A1/fr active Application Filing
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