EP2668307B1 - Formung eines ferromagnetischen metallglases durch schnelle kondensatorentladung - Google Patents

Formung eines ferromagnetischen metallglases durch schnelle kondensatorentladung Download PDF

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Publication number
EP2668307B1
EP2668307B1 EP12739639.8A EP12739639A EP2668307B1 EP 2668307 B1 EP2668307 B1 EP 2668307B1 EP 12739639 A EP12739639 A EP 12739639A EP 2668307 B1 EP2668307 B1 EP 2668307B1
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European Patent Office
Prior art keywords
sample
temperature
metallic glass
heating
electrical energy
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English (en)
French (fr)
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EP2668307A4 (de
EP2668307A2 (de
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Georg Kaltenboeck
Joseph P. Schramm
Marios D. Demetriou
William L. Johnson
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California Institute of Technology CalTech
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California Institute of Technology CalTech
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Priority claimed from PCT/US2012/023177 external-priority patent/WO2012103552A2/en
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Publication of EP2668307A4 publication Critical patent/EP2668307A4/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/13—Modifying the physical properties of iron or steel by deformation by hot working
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/34—Methods of heating
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/34—Methods of heating
    • C21D1/40—Direct resistance heating
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D11/00—Process control or regulation for heat treatments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/03—Amorphous or microcrystalline structure

Definitions

  • This invention relates generally to a novel method of forming metallic glass; and more particularly to a process for forming ferromagnetic metallic glasses using rapid capacitor discharge heating.
  • Amorphous materials are a new class of engineering material, which have a unique combination of high strength, elasticity, corrosion resistance and processability from the molten state.
  • Amorphous materials differ from conventional crystalline alloys in that their atomic structure lacks the typical long-range ordered patterns of the atomic structure of conventional crystalline alloys.
  • Amorphous materials are generally processed and formed by cooling a molten alloy from above the melting temperature of the crystalline phase (or the thermodynamic melting temperature) to below the "glass transition temperature” of the amorphous phase at "sufficiently fast" cooling rates, such that the nucleation and growth of alloy crystals is avoided.
  • the processing methods for amorphous alloys have always been concerned with quantifying the "sufficiently fast cooling rate", which is also referred to as “critical cooling rate", to ensure formation of the amorphous phase.
  • the "critical cooling rates" for early amorphous materials were extremely high, on the order of 10 6 °C/sec. As such, conventional casting processes were not suitable for such high cooling rates, and special casting processes such as melt spinning and planar flow casting were developed. Due to the crystallization kinetics of those early alloys being substantially fast, extremely short time (on the order of 10 -3 seconds or less) for heat extraction from the molten alloy were required to bypass crystallization, and thus early amorphous alloys were also limited in size in at least one dimension. For example, only very thin foils and ribbons (order of 25 microns in thickness) were successfully produced using these conventional techniques. Because the critical cooling rate requirements for these amorphous alloys severely limited the size of parts made from amorphous alloys, the use of early amorphous alloys as bulk objects and articles was limited.
  • This cooling has either been realized using a single-step monotonous cooling operation or a multi-step process.
  • metallic molds made of copper, steel, tungsten, molybdenum, composites thereof, or other high conductivity materials
  • these conventional processes are not suitable for forming larger bulk objects and articles of a broader range of bulk-solidifying amorphous alloys.
  • the metallic glass alloy should either exhibit an even higher stability against crystallization when heated by conventional heating, or be heated at an unconventionally high heating rate which would extend the temperature range of stability and lower the process viscosity to values typical of those used in processing thermoplastics.
  • thermodynamic and transport properties such as heat capacity and viscosity
  • Typical measurement instruments such as Differential Scanning Calorimeters, Thermo-Mechanical Analyzers, and Couette Viscometers rely on conventional heating instrumentation, such as electric and induction heaters, and are thus capable of attaining sample heating rates that are considered conventional (typically ⁇ 100°C/min).
  • metallic supercooled liquids can be stable against crystallization over a limited temperature range when heated at a conventional heating rate, and thus the measureable thermodynamic and transport properties are limited to within the accessible temperature range.
  • RCDF rapid capacitor discharge heating
  • the invention is directed to a method of rapidly heating and shaping a ferromagnetic metallic glass using a rapid capacitor discharge wherein a quantum of electrical energy is discharged uniformly through a substantially defect free sample having a substantially uniform cross-section to rapidly and uniformly heat the entirety of the sample to a processing temperature between the glass transition temperature of the amorphous phase and the equilibrium melting temperature of the alloy and simultaneously shaping and then cooling the sample into an amorphous article.
  • the sample is preferably heated to the processing temperature at a rate of at least 500 K/sec.
  • the step of shaping uses a conventional forming technique, such as, for example, injection molding, dynamic forging, stamp forging and blow molding.
  • the ferromagnetic metallic glass is selected with a relative change of resistivity per unit of temperature change (S) of about 1 x 10 -40 C -1 .
  • the ferromagnetic metallic glass is an alloy based on an elemental metal selected from the group consisting of Zr, Pd, Pt, Au, Fe, Co, Ti, Al, Mg, Ni and Cu.
  • the quantum of electrical energy is discharged into the sample through at least two electrodes connected to opposite ends of said sample in a manner such that the electrical energy is introduced into the sample uniformly.
  • the method uses a quantum of electrical energy of at least 100 Joules.
  • the processing temperature is about half-way between the glass transition temperature of the ferromagnetic metallic glass and the equilibrium melting point of the alloy. In one such embodiment, the processing temperature is at least 200 K above the glass transition temperature of the ferromagnetic metallic glass. In one such embodiment, the processing temperature is such that the viscosity of the heated ferromagnetic metallic glass is between about 1 to 10 4 Pas-sec.
  • the forming pressure used to shape the sample is controlled such that the sample is deformed at a rate sufficiently slow to avoid high Weber-number flow.
  • the deformational rate used to shape the sample is controlled such that the sample is deformed at a rate sufficiently slow to avoid high Weber-number flow.
  • the initial amorphous metal sample (feedstock) may be of any shape with a uniform cross section such as, for example, a cylinder, sheet, square and rectangular solid.
  • the contact surfaces of the amorphous metal sample are cut parallel and polished flat in order to ensure good contact with the electrode contact surface.
  • the sample of amorphous material has a substantially uniform cross-section.
  • at least two electrodes connect a source of electrical energy to the sample of amorphous material.
  • the electrodes are attached to the sample such that substantially uniform connections are formed between the electrodes and the sample.
  • the electromagnetic skin depth of the dynamic electric field is large compared to the radius, width, thickness and length of the charge.
  • the electrode material is chosen to be a metal with a low yield strength and high electrical and thermal conductivity such as, for example, copper, silver or nickel, or alloys formed with at least 95 at% of copper, silver or nickel.
  • a "seating" pressure is applied between the electrodes and the initial amorphous sample in order to plastically deform the contact surface of the electrode at the electrode/sample interface to conform it to the microscopic features of the contact surface of the sample.
  • a low-current "seating" electrical pulse is applied between the electrodes and the initial amorphous sample in order to locally soften any non-contact regions of the amorphous sample at the contact surface of the electrode, and thus conform it to the microscopic features of the contact surface of the electrode.
  • the source of electrical energy is capable of producing a quantum of electrical energy sufficient to uniformly heat the entirety of the sample to a processing temperature between the glass transition temperature of the amorphous phase and the equilibrium melting temperature of the alloy at a rate of at least 500 K/sec.
  • the source of electrical energy is discharged at a rate such that the sample is adiabatically heated, or in other words at a rate much higher than the thermal relaxation rate of the amorphous metal sample, in order to avoid thermal transport and development of thermal gradients and thus promote uniform heating of the sample.
  • the shaping tool used in the apparatus is selected from the group consisting of an injection mold, a dynamic forge, a stamp forge and a blow mold, and is capable of imposing a deformational strain sufficient to form said heated sample.
  • the shaping tool is at least partially formed from at least one of the electrodes.
  • the shaping tool is independent of the electrodes.
  • a pneumatic or magnetic drive system for applying the deformational force to the sample.
  • the deformational force or deformational rate can be controlled such that the heated amorphous material is deformed at a rate sufficiently slow to avoid high Weber-number flow.
  • the shaping tool further comprises a heating element for heating the tool to a temperature preferably around the glass transition temperature of the amorphous material.
  • a heating element for heating the tool to a temperature preferably around the glass transition temperature of the amorphous material.
  • the surface of the formed liquid will be cooled more slowly thus improving the surface finish of the article being formed.
  • a tensile deformational force is applied on an adequately-gripped sample during the discharge of energy in order to draw a wire or fiber of uniform cross section.
  • the tensile deformational force is controlled so that the flow of the material is Newtonian and failure by necking is avoided.
  • the tensile deformational rate is controlled so that the flow of the material is Newtonian and failure by necking is avoided.
  • a stream of cold helium is blown onto the drawn wire or fiber to facilitate cooling below glass transition.
  • a rapid capacitor discharge apparatus for measuring thermodynamic and transport properties of the supercooled liquid over the entire range of its metastability.
  • a high-resolution and high-speed thermal imaging camera is used to simultaneously record the uniform heating and uniform deformation of a sample of amorphous metal.
  • the temporal, thermal, and deformational data can be converted into time, temperature, and strain data, while the input electrical power and imposed pressure can be converted into internal energy and applied stress, thereby yielding information concerning the temperature, temperature dependent viscosity, heat capacity and enthalpy of the sample.
  • the invention is directed to a method of rapidly and uniformly heating a ferromagnetic metallic glass using a rapid capacitor discharge including:
  • the time constant of the discharge is controlled by increasing the inductance of the electrical circuit.
  • the inductance may be increased by adding a source of additional inductance in series with the sample.
  • the time constant of the discharge is controlled by increasing the capacitance of the electrical circuit.
  • the method also includes pre-heating the sample to a pre-heating temperature above the Curie temperature prior to discharging the quantum of electrical energy.
  • the pre-heating temperature is preferably above the Curie temperature and below the glass transition temperature.
  • the pre-heating temperature is obtained using a capacitive discharge pulse.
  • a rapid capacitor discharge apparatus for rapidly heating a magnetic amorphous metal including:
  • the time constant of the discharge may be modified by adding additional inductance to the electrical circuit.
  • the time constant of the discharge may be modified by adding at least one additional inductor in series with the source.
  • the time constant of the discharge may be modified by adding additional capacitance to the electrical circuit.
  • the source is further configured to supply a pre-heating discharge configured to pre-heat the sample to a pre-heating temperature above the Curie temperature prior to discharging the quantum of electrical energy.
  • the pre-heating temperature is preferably above the Curie temperature and below the glass transition temperature.
  • the current invention is directed to a method of uniformly heating, rheologically softening, and thermoplastically forming metallic glasses rapidly (typically with processing times of less than 1 second into a net shape article using an extrusion or mold tool by Joule heating. More specifically, the method utilizes the discharge of electrical energy (typically 100 Joules to 100 KJoules) stored in a capacitor to uniformly and rapidly heat a sample or charge of metallic glass alloy to a predetermined "process temperature" about half-way between the glass transition temperature of the amorphous material and the equilibrium melting point of the alloy in a time scale of several milliseconds or less, and is referred to hereinafter as rapid capacitor discharge forming (RCDF).
  • electrical energy typically 100 Joules to 100 KJoules
  • the RCDF process of the current invention proceeds from the observation that metallic glass, by its virtue of being a frozen liquid, has a relatively low electrical resistivity, which can result in high dissipation and efficient, uniform heating of the material at rate such that the sample is adiabatically heated with the proper application of an electrical discharge.
  • the RCDF method By rapidly and uniformly heating a BMG, the RCDF method extends the stability of the supercooled liquid against crystallization to temperatures substantially higher than the glass transition temperature, thereby bringing the entire sample volume to a state associated with a processing viscosity that is optimal for forming.
  • the RCDF process also provides access to the entire range of viscosities offered by the metastable supercooled liquid, as this range is no longer limited by the formation of the stable crystalline phase. In sum, this process allows for the enhancement of the quality of parts formed, an increase yield of usable parts, a reduction in material and processing costs, a widening of the range of usable BMG materials, improved energy efficiency, and lower capital cost of manufacturing machines.
  • thermodynamic and transport properties throughout the entire range of the liquid metastability become accessible for measurement. Therefore by incorporating additional standard instrumentation to a Rapid Capacitor Discharge set up such as temperature and strain measurement instrumentation, properties such as viscosity, heat capacity and enthalpy can be measured in the entire temperature range between glass transition and melting point.
  • FIG. 1 A simple flow chart of the RCDF technique of the current invention is provided in FIG. 1 . As shown, the process begins with the discharge of electrical energy (typically 100 Joules to 100 KJoules) stored in a capacitor into a sample block or charge of metallic glass alloy.
  • electrical energy typically 100 Joules to 100 KJoules
  • the application of the electrical energy may be used to rapidly and uniformly heat the sample to a predetermined "process temperature" above the glass transition temperature of the alloy, and more specifically to a processing temperature about half-way between the glass transition temperature of the amorphous material and the equilibrium melting point of the alloy ( ⁇ 200- 300 K above Tg), on a time scale of several microseconds to several milliseconds or less, such that the amorphous material has a process viscosity sufficient to allow facile shaping ( ⁇ 1 to 10 4 Pas-s or less).
  • the sample may be shaped into a high quality amorphous bulk article via any number of techniques including, for example, injection molding, dynamic forging, stamp forging, blow molding, etc.
  • any number of techniques including, for example, injection molding, dynamic forging, stamp forging, blow molding, etc.
  • the ability to shape a charge of metallic glass depends entirely on ensuring that the heating of the charge is both rapid and uniform across the entire sample block. If uniform heating is not achieved, then the sample will instead experience localized heating and, although such localized heating can be useful for some techniques, such as, for example, joining or spot-welding pieces together, or shaping specific regions of the sample, such localized heating has not and cannot be used to perform bulk shaping of samples.
  • sample heating is not sufficiently rapid (typically on the order of 500 - 10 5 K/s) then either the material being formed will lose its amorphous character, or the shaping technique will be limited to those amorphous materials having superior processability characteristics (i.e., high stability of the supercooled liquid against crystallization), again reducing the utility of the process.
  • the RCDF method of the current invention ensures the rapid uniform heating of a sample.
  • S a relative change of resistivity per unit of temperature change coefficient
  • a typical amorphous material has a large po (80 ⁇ -cm ⁇ po ⁇ 300 ⁇ -cm), but a very small (and frequently negative) value of S (-1 x 10 -4 ⁇ S ⁇ +1 x 10 -4 ).
  • T F T F 0 + E / C S
  • R is the total resistance of the sample (plus output resistance of the capacitive discharge circuit.
  • common crystalline metals have much lower po (1- 30 ⁇ -cm) and much greater values of S ⁇ 0.01 - 0.1. This leads to significant differences in behavior. For example, for common crystalline metals such as copper alloys, aluminum, or steel alloys, po is much smaller (1-20 ⁇ -cm) while S is much larger, typically S ⁇ 0.01 - 0.1. The smaller po values in crystalline metals will lead to smaller dissipation in the sample (compared with the electrodes) and make the coupling of the energy of the capacitor to the sample less efficient. Furthermore, when a crystalline metal melts, p(T) generally increases by a factor of 2 or more on going from the solid metal to the molten metal.
  • the crystalline sample will invariably melt locally, typically in the vicinity of the high voltage electrode or other interface within the sample.
  • a capacitor discharge of energy through a crystalline rod leads to spatial localization of heating and localized melting wherever the initial resistance was greatest (typically at interfaces). In fact, this is the basis of capacitive discharge welding (spot welding, projection welding, "stud welding” etc.) of crystalline metals where a local melt pool is created near the electrode/sample interface or other internal interface within the parts to be welded.
  • Stability of the sample with respect to development of inhomogeneity in power dissipation during dynamic heating can be understood by carrying out stability analysis which includes Ohmic "Joule” heating by the current and heat flow governed by the Fourier equation.
  • stability analysis which includes Ohmic "Joule” heating by the current and heat flow governed by the Fourier equation.
  • a sample with resistivity which increases with temperature (i.e., positive S)
  • a local temperature variation along the axis of the sample cylinder will increase local heating, which further increases the local resistance and heat dissipation.
  • crystalline materials it results in localized melting. Whereas this behavior is useful in welding where one wishes to produce local melting along interfaces between components, this behavior is extremely undesirable if one wishes to uniformly heat an amorphous material.
  • the present invention provides a critical criterion to ensure uniform heating.
  • D the thermal diffusivity (m 2 /s) of the amorphous material
  • Cs the total heat capacity of the sample
  • Ro the total resistance of the sample.
  • D and Cs typical of metallic glass, and assuming a length (L ⁇ 1cm), and an input power I 2 R 0 ⁇ 10 6 Watts, typically required for the present invention, it is possible to obtain a S crit ⁇ 10 -4 - 10 -5 .
  • This criterion for uniform heating should be satisfied for many metallic glasses (see above S values).
  • the sample be substantially free of defects and formed with a uniform cross-section. If these conditions are not met, the heat will not dissipate evenly across the sample and localized heating will occur. Specifically, if there is a discontinuity or defect in the sample block then the physical constants (i.e., D and C s ) discussed above will be different at those points leading to differential heating rates. In addition, because the thermal properties of the sample also are dependent on the dimensions of the item (i.e., L) if the cross-section of the item changes then there will be localized hot spots along the sample block.
  • the thermal properties of the sample also are dependent on the dimensions of the item (i.e., L) if the cross-section of the item changes then there will be localized hot spots along the sample block.
  • the sample block is formed such that it is substantially free of defects and has a substantially uniform cross-section. It should be understood that though the cross-section of the sample block should be uniform, as long as this requirement is met there are no inherent constraints placed on the shape of the block.
  • the block may take any suitable geometrically uniform shape, such as a sheet, block, cylinder, etc.
  • the sample contact surfaces are cut parallel and polished flat in order to ensure good contact with the electrodes.
  • the electrode/sample interface must be designed to ensure that the electrical charge is applied evenly, i.e., with uniform density, such that no "hot points" develop at the interface. For example, if different portions of the electrode provide differential conductive contact with the sample, spatial localization of heating and localized melting will occur wherever the initial resistance is greatest. This in turn will lead to discharge welding where a local melt pool is created near the electrode/sample interface or other internal interface within the sample.
  • the electrodes are polished flat and parallel to ensure good contact with the sample.
  • the electrodes are made of a soft metal, and uniform "seating" pressure is applied that exceeds the electrode material yield strength at the interface, but not the electrode buckling strength, so that the electrode is positively pressed against the entire interface yet unbuckled, and any non-contact regions at the interface are plastically deformed.
  • a uniform low-energy "seating" pulse is applied that is barely sufficient to raise the temperature of any non-contact regions of the amorphous sample at the contact surface of the electrode to slightly above the glass transition temperature of the amorphous material, and thus allowing the amorphous sample to conform to the microscopic features of the contact surface of the electrode.
  • the electrodes are positioned such that positive and negative electrodes provide a symmetric current path through the sample.
  • Some suitable metals for electrode material are Cu, Ag and Ni, and alloys made substantially of Cu, Ag and Ni (i.e., that contain at least 95 at% of these materials).
  • the sample will heat up uniformly if heat transport towards the cooler surrounding and electrodes is effectively evaded, i.e., if adiabatic heating is achieved.
  • dT/dt has to be high enough, or ⁇ RC small enough, to ensure that thermal gradients due to thermal transport do not develop in the sample.
  • the basic RCDF shaping tool includes a source of electrical energy (10) and two electrodes (12).
  • the electrodes are used to apply a uniform electrical energy to a sample block (14) of uniform cross-section made of an amorphous material having an S crit value sufficiently low and a has a large po value sufficiently high, to ensure uniform heating.
  • the uniform electrical energy is used to uniformly heat the sample to a predetermined "process temperature" above the glass transition temperature of the alloy in a time scale of several milliseconds or less.
  • the viscous liquid thus formed is simultaneously shaped in accordance with a preferred shaping method, including, for example, injection molding, dynamic forging, stamp forging blow molding, etc. to form an article on a time scale of less than one second.
  • any source of electrical energy suitable for supplying sufficient energy of uniform density to rapidly and uniformly heat the sample block to the predetermined process temperature such as, for example, a capacitor having a discharge time constant of from 10 ⁇ s to 10 milliseconds may be used.
  • any electrodes suitable for providing uniform contact across the sample block may be used to transmit the electrical energy.
  • the electrodes are formed of a soft metal, such as, for example, Ni, Ag, Cu, or alloys made using at least 95 at% of Ni, Ag and Cu, and are held against the sample block under a pressure sufficient to plastically deform the contact surface of the electrode at the electrode/sample interface to conform it to the microscopic features of the contact surface of the sample block.
  • the current invention is also directed to an apparatus for shaping a sample block of amorphous material.
  • an injection molding apparatus may be incorporated with the RCDF method.
  • the viscous liquid of the heated amorphous material is injected into a mold cavity (18) held at ambient temperature using a mechanically loaded plunger to form a net shape component of the metallic glass.
  • a mold cavity (18) held at ambient temperature using a mechanically loaded plunger to form a net shape component of the metallic glass.
  • the charge is located in an electrically insulating "barrel” or “shot sleeve” and is preloaded to an injection pressure (typically 1-100 MPa) by a cylindrical plunger made of a conducting material (such as copper or silver) having both high electrical conductivity and thermal conductivity.
  • the plunger acts as one electrode of the system.
  • the sample charge rests on an electrically grounded base electrode.
  • the stored energy of a capacitor is discharged uniformly into the cylindrical metallic glass sample charge provided that certain criteria discussed above are met.
  • the loaded plunger then drives the heated viscous melt into the net shape mold cavity.
  • any suitable shaping technique may be used.
  • Some alternative exemplary embodiments of other shaping methods that may be used in accordance with the RCDF technique are provided in FIGs. 3 to 5 , and discussed below.
  • a dynamic forge shaping method may be used.
  • the sample contacting portions (20) of the electrodes (22) would themselves form the die tool.
  • the cold sample block (24) would be held under a compressive stress between the electrodes and when the electrical energy is discharged the sample block would become sufficiently viscous to allow the electrodes to press together under the predetermined stress thereby conforming the amorphous material of the sample block to the shape of the die (20).
  • a stamp form shaping method is proposed.
  • the electrodes (30) would clamp or otherwise hold the sample block (32) between them at either end.
  • a thin sheet of amorphous material is used, although it should be understood that this technique may be modified to operate with any suitable sample shape.
  • the forming tool or stamp (34) which as shown comprises opposing mold or stamp faces (36), would be brought together with a predetermined compressive force against portion of the sample held therebetween, thereby stamping the sample block into the final desired shape.
  • a blow mold shaping technique could be used.
  • the electrodes (40) would clamp or otherwise hold the sample block (42) between them at either end.
  • the sample block would comprise a thin sheet of material, although any shape suitable may be used. Regardless of its initial shape, in the exemplary technique the sample block would be positioned in a frame (44) over a mold (45) to form a substantially air-tight seal, such that the opposing sides (46 and 48) of the block (i.e., the side facing the mold and the side facing away from the mold) can be exposed to a differential pressure, i.e., either a positive pressure of gas or a negative vacuum.
  • a differential pressure i.e., either a positive pressure of gas or a negative vacuum.
  • a fiber-drawing technique could be used.
  • the electrodes (49) would be in good contact with the sample block (50) near either end of the sample, while a tensile force will be applied at either end of the sample.
  • a stream of cold helium (51) is blown onto the drawn wire or fiber to facilitate cooling below glass transition.
  • the sample block would comprise a cylindrical rod, although any shape suitable may be used. Upon discharge of the electrical energy through the sample block, the sample becomes viscous and stretches uniformly under the stress of the tensile force, thereby drawing the sample block into a wire or fiber of uniform cross section.
  • the sample (52) would be held under a compressive stress between two paddle shaped electrodes (53), while a thermal imaging camera (54) is focused on the sample.
  • the camera When the electrical energy is discharged, the camera will be activated and the sample block would be simultaneously charged. After the sample becomes sufficiently viscous, the electrodes will press together under the predetermined pressure to deform the sample.
  • the simultaneous heating and deformation process may be captured by a series of thermal images.
  • the temporal, thermal, and deformational data can be converted into time, temperature, and strain data, while the input electrical power and imposed pressure can be converted into internal energy and applied stress, thereby yielding information of the temperature, and temperature-dependent viscosity, heat capacity and enthalpy of the sample.
  • the above discussion has focused on the essential features of a number of exemplary shaping techniques, it should be understood that other shaping techniques may be used with the RCDF method of the current invention, such as extrusion or die casting. Moreover, additional elements may be added to these techniques to improve the quality of the final article. For example, to improve the surface finish of the articles formed in accordance with any of the above shaping methods the mold or stamp may be heated to around or just below the glass transition temperature of the amorphous material, thereby smoothing surface defects.
  • the compressive force, and in the case of an injection molding technique the compressive speed, of any of the above shaping techniques may be controlled to avoid melt front instability arising from high "Weber number" flows, i.e., to prevent atomization, spraying, flow lines, etc.
  • the RCDF shaping techniques and alternative embodiments discussed above may be applied to the production of small, complex, net shape, high performance metal components such as casings for electronics, brackets, housings, fasteners, hinges, hardware, watch components, medical components, camera and optical parts, jewelry etc.
  • the RCDF method can also be used to produce small sheets, tubing, panels, etc. which could be dynamically extruded through various types of extrusion dyes used in concert with the RCDF heating and injection system.
  • the RCDF technique of the current invention provides a method of shaping amorphous alloys that allows for the rapid uniform heating of a wide range of amorphous materials and that is relatively cheap and energy efficient.
  • the advantages of the RCDF system are described in greater detail below.
  • Thermoplastic molding and forming of BMGs is severely restricted by the tendency of BMGs to crystallize when heated above their glass transition temperature, Tg.
  • Tg glass transition temperature
  • the rate of crystal formation and growth in the undercooled liquid above T g increases rapidly with temperature while the viscosity of the liquid falls.
  • ⁇ T 30 - 150°C.
  • This ⁇ T determines the maximum temperature and lowest viscosity for which the liquid can be thermoplastically processed.
  • the viscosity is constrained to be larger than ⁇ 10 4 Pa-s, more typically 10 5 -10 7 Pa-s, which severely limits net shape forming.
  • the amorphous material sample can be uniformly heated and simultaneously formed (with total required processing times of milliseconds) at heating rates ranging from 10 4 - 10 7 C/s.
  • the sample can be thermoplastically formed to net shape with much larger ⁇ T and as a result with much lower process viscosities in the range of 1 to 10 4 Pa-s, which is the range of viscosities used in the processing of plastics. This requires much lower applied loads, shorter cycle times, and will result in much better tool life.
  • alloys with small ⁇ T or alloys having much faster crystallization kinetics and in turn far poorer glass forming ability, can be processed using RCDF.
  • cheaper and otherwise more desirable alloys based on Zr, Pd, Pt, Au, Fe, Co, Ti, Al, Mg, Ni and Cu and other inexpensive metals are rather poor glass formers with small ⁇ T and strong tendency to crystallize.
  • These "marginal glass forming" alloys cannot be thermoplastically processed using any of the currently practiced methods, but could easily be used with the RCDF method of the current invention.
  • Competing manufacturing technologies such as die-casting, permanent-mold casting, investment casting and metal powder injection molding (PIM), are inherently far less energy efficient.
  • RCDF the energy consumed is only slightly greater than that required to heat the sample to the desired process temperature.
  • Hot crucibles, RF induction melting systems, etc. are not required. Further, there is no need to pour molten alloy from one container to another thereby reducing the processing steps required and the potential for material contamination and material loss.
  • RCDF manufacturing equipment would be small, compact, clean, and would lend itself readily to automation with a minimum of moving parts and an essentially all "electronic" process.
  • the millisecond time scales required to process a sample by RCDF will result in minimal exposure of the heated sample to ambient air. As such, the process could be carried out in the ambient environment as opposed to current process methods where extended air exposure gives severe oxidation of the molten metal and final part.
  • Small right circular cylinders of several BMG materials were fabricated with diameters of 1-2 mm and heights of 2-3 mm.
  • the sample mass ranged from ⁇ 40 mg to about ⁇ 170 mg and was selected to obtain T F well above the glass transition temperature of the particular BMG.
  • the BMG materials were a Zr-Ti-based BMG (Vitreloy 1, a Zr-Ti-Ni-Cu-Be BMG), a Pd-based BMG (Pd-Ni-Cu-P alloy), and an Fe-based BMG (Fe-Cr-Mo-P-C) having glass transitions (Tg) at 340C, 300 C, and ⁇ 430 C respectively. All of these metallic glasses have S ⁇ -1 x 10 -4 ⁇ S crit .
  • FIGs. 8a to 8d show the results of a series of tests on Pd-alloy cylinders of radius 2mm and height 2mm (8a).
  • the degree of plastic flow in the BMG was quantified by measuring the initial and final heights of the processed samples. It is particularly important to note that the samples are not observed to bond to the copper electrode during processing. This can be attributed to the high electrical and thermal conductivity of copper compared to the BMG.
  • the copper never reaches sufficiently high temperature to allow wetting by the "molten" BMG during the time scale of processing ( ⁇ milliseconds). Further, it should be noted that there is little or no damage to the electrode surface.
  • the final processed samples were freely removed from the copper electrode following processing and are shown in FIG. 9 with a length scale reference.
  • the initial and final cylinder heights were used to determine the total compressive strain developed in the sample as it deformed under load.
  • the engineering "strain" is given by Ho/H where Ho and H are the initial (final) height of the sample cylinder respectively.
  • the true strain is given by ln(H 0 /H).
  • the results are plotted vs. discharge energy in FIG. 10 . These results indicated that the true strain appears to be a roughly linear increasing function of the energy discharged by the capacitor.
  • a working prototype RCDF injection molding apparatus was constructed. Schematics of the device are provided in FIGs. 11a to 11e . Experiments conducted with the shaping apparatus prove that it can be used to injection mold charges of several grams into net-shape articles in less than one second.
  • the system as shown is capable of storing an electrical energy of ⁇ 6 KJoules and applying a controlled process pressure of up to ⁇ 100 MPa to be used to produce small net shape BMG parts.
  • the entire machine is comprised of several independent systems, including an electrical energy charge generation system, a controlled process pressure system, and a mold assembly.
  • the electrical energy charge generation system comprises a capacitor bank, voltage control panel and voltage controller all interconnected to a mold assembly (60) via a set of electrical leads (62) and electrodes (64) such that an electrical discharge of may be applied to the sample blank through the electrodes.
  • the controlled process pressure system (66) includes an air supply, piston regulator, and pneumatic piston all interconnected via a control circuit such that a controlled process pressure of up to ⁇ 100 MPa may be applied to a sample during shaping.
  • the shaping apparatus also includes the mold assembly (60), which will be described in further detail below, but which is shown in this figure with the electrode plunger (68) in a fully retracted position.
  • the total mold assembly is shown removed from the larger apparatus in FIGs. 11b .
  • the total mold assembly includes top and bottom mold blocks (70a and 70b), the top and bottom parts of the split mold (72a and 72b), electrical leads (74) for carrying the current to the mold cartridge heaters (76), an insulating spacer (78), and the electrode plunger assembly (68) in this figure shown in the "fully depressed" position.
  • a sample block of amorphous material (80) is positioned inside the insulating sleeve (78) atop the gate to the split mold (82).
  • This assembly is itself positioned within the top block (72a) of the mold assembly (60).
  • the electrode plunger (not shown) would then be positioned in contact with the sample block (80) and a controlled pressure applied via the pneumatic piston assembly.
  • the split mold (60) takes the form of a ring (86). Sample rings made of a Pd 43 Ni 10 Cu 27 P 20 amorphous material formed using the exemplary RCDF apparatus of the current invention are shown in FIGs. 12a and 12b .
  • the RCDF method of the current invention can be used to heat and shape a wide-variety of metallic glasses utilizing dissipation of electrical current to uniformly heat a metallic glass charge at time scales far shorter than typical times associated with crystallization.
  • a typical discharge time ⁇ RC utilized in RDHF is on the order of 1 ms.
  • the skin depth would be about 40 mm. Since such a skin depth is much larger than the available useful size of a metallic glass, uniform heating would be ensured.
  • ferromagnetic metallic glasses typically have much higher relative permeability ( ⁇ r of 10 2 -10 4 ) leading to skin depths, A, in the range of 0.5 to 5 mm. These skin depths therefore fall within the useful sizes for a metallic glass charge. Consequently, non-uniform heating will occur when processing ferromagnetic glasses using RCDF operating at conventional time scales on the order of 1 ms.
  • the invention is directed to achieving relatively large electromagnetic skin depths comparable to those achieved in the processing of nonmagnetic metallic glasses by lengthening the time of the pulse, therefore increasing the time constant associate with the rise of the current pulse ⁇ , and consequently, increasing the skin depth, A.
  • This will enable metallic glass alloys with high relative permeability to be heated uniformly using capacitive discharge.
  • the pulse rise time should not approach or exceed the time associated with crystallizing the metallic glass at the optimum forming temperature in the undercooled liquid region (typically between 0.1-1 s for ferromagnetic glasses).
  • the rise time of the pulse of the capacitive discharge ⁇ is lengthened, therefore decreasing the frequency applied to the metallic glass charge and increasing the skin depth A.
  • the skin depth can be increased by stretching the pulse rise time as follows:
  • the skin depth can also be increased by raising the temperature of the metallic glass charge before the rapid discharge takes place.
  • the relative permeability drops with increasing temperature, and reaches values of approximately 1 at temperatures above the Curie temperature.
  • Curie temperatures of ferromagnetic glasses are typically below their glass transition, such that it enables pre-heating to low permeability values without any plastic forming or crystallization taking place.
  • a ferromagnetic metallic glass charge is heated by a relatively slow capacitive discharge pulse to a temperature above the Curie temperature, but below the glass transition temperature, and then submitted to a rapid capacitive discharge for subsequent heating and forming.
  • FIGs. 13 and 14 One exemplary result obtained shaping a magnetic metallic glass in accordance with the current embodiment is shown in FIGs. 13 and 14 .
  • the effect of the pulse frequency (or pulse rise time) on the forming of ferromagnetic glasses has been investigated by studying the shaping of rod-shaped charge to form disks.
  • Two amorphous rods 4 mm in diameter and about 6 mm in length having the ferromagnetic glass composition Fe 68 Cr 2 Mo 5 Ni 5 P 12.5 C 5 B 2.5 were utilized as charge.
  • An example of such a charge is shown in FIG 13a .
  • An electrical energy density of about 3850 J/cc was discharged across both samples, while a compressive force of about 300 N was applied simultaneously with the discharge.
  • samples A and B are presented in FIGs. 14b and 14c .
  • a high frequency (short rise time ⁇ ) associated with a smaller inductance and capacitance results in a part of highly non-uniform shape (sample A); a consequence of highly non-uniform heating attributed to the skin depth being small compared to the charge size.
  • a low frequency (long rise time ⁇ ) associated with a larger inductance and capacitance results in a fairly uniform disk-shaped part (sample B); a consequence of a fairly uniform heating associated with a larger skin depth.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Forging (AREA)
  • Manufacturing Of Steel Electrode Plates (AREA)

Claims (15)

  1. Verfahren zum schnellen und gleichmäßigen Erwärmen eines ferromagnetischen Metallglases unter Verwendung einer Schnellentladung eines Kondensators umfassend:
    Bereitstellen einer Probe eines ferromagnetischen Metallglases, welches aus einer Metallglas bildenden Legierung gebildet ist, welche im Wesentlichen einen gleichmäßigen Querschnitt aufweist;
    Platzieren der Probe in elektrischen Kontakt mit einer elektrischen Energiequelle, die in der Lage ist, ein Quantum elektrischer Energie zu erzeugen;
    Entladen eines Quantums elektrischer Energie gleichmäßig durch die Probe, um die Probe schnell und gleichmäßig auf eine Verarbeitungstemperatur zwischen der Glasübergangstemperatur des Metallglases und dem Gleichgewichtsschmelzpunkt der Metallglas bildenden Legierung zu erhitzen, wobei das Entladen des Quantums elektrischer Energie ein elektrisches Feld in der Probe erzeugt, und wobei die elektromagnetische Hauttiefe des erzeugten dynamischen elektrischen Feldes groß ist verglichen mit dem Radius der Breite, der Dicke und der Länge der Probe, aber wobei die Anstiegszeit des Stromimpulses nicht die Zeit überschreitet, die mit einem Kristallisieren der Probe bei der optimalen Bildungstemperatur in der unterkühlten Flüssigkeitsregion assoziiert ist;
    Anwenden einer Umformkraft, um die erhitzte Probe zu formen, während die erhitzte Probe weiterhin bei einer Temperatur zwischen der Glasübergangstemperatur des Metallglases und dem Gleichgewichtsschmelzpunkt der Metallglas bildenden Legierung, ist; und
    Abkühlen der Probe auf eine Temperatur unter der Glasübergangstemperatur des Metallglases.
  2. Verfahren nach Anspruch 1, wobei die Temperatur der Probe mit einer Rate von zumindest 500 K/sec erhöht wird.
  3. Verfahren nach Anspruch 1, wobei das Metallglas eine relative Widerstandsänderung pro Temperaturänderungseinheit (S) aufweist, welche nicht größer ist als 1 x 10-4 °C-1 und ein Widerstand bei Raumtemperatur (ρ0) zwischen 80 und 300 µΩ-cm.
  4. Verfahren nach Anspruch 1, wobei das Quantum elektrischer Energie zumindest 100 J ist und die Anstiegszeit des Stromimpulses zwischen 1 ms und 100 ms ist.
  5. Verfahren nach Anspruch 1, wobei die Verarbeitungstemperatur ungefähr dem halben Weg zwischen der Glasübergangstemperatur des Metallglases und des Gleichgewichtsschmelzpunktes der Metallglas bildenden Legierung ist.
  6. Verfahren nach Anspruch 1, wobei die Verarbeitungstemperatur so ist, dass die Viskosität des geheizten Metallglases von 1 bis 104 Pa-s ist.
  7. Verfahren nach Anspruch 1, wobei die Anstiegszeit des Stromimpulses gesteuert wird durch Erhöhen der Induktivität der elektrischen Schaltung.
  8. Verfahren nach Anspruch 7, wobei die Induktivität erhöht wird durch Hinzufügen einer Spule in Serie mit der Probe.
  9. Verfahren nach Anspruch 1, wobei die Zeitkonstante der Entladung gesteuert wird durch Erhöhen der Kapazität der elektrischen Schaltung.
  10. Verfahren nach Anspruch 1, ferner umfassend ein Vorheizen der Probe auf eine Vorheiztemperatur über der Curie-Temperatur vor dem Entladen des Quantums elektrischer Energie.
  11. Verfahren nach Anspruch 10, wobei die Vorheiztemperatur über der Curie-Temperatur ist und unter der Glasübergangstemperatur ist.
  12. Verfahren nach Anspruch 10, wobei der Vorheizprozess unter Verwendung eines kapazitiven Entladeimpulses durchgeführt wird.
  13. Verfahren nach Anspruch 1, wobei der Entladeschritt des Quantums elektrischer Energie durch zumindest zwei Elektroden auftritt, die an entgegengesetzten Enden der Probe verbunden sind.
  14. Verfahren nach Anspruch 1, wobei die Umformkraft auf das erhitzte Metallglas angewendet wird, nachdem das Entladen der elektrischen Energie abgeschlossen ist.
  15. Verfahren nach Anspruch 11, wobei die Anwendung der Umformkraft gesteuert wird durch einen Betätigungsmechanismus, welcher Spannungs-/Stromerfassung mit pneumatischer, hydraulischer, magnetischer oder elektrischer Bewegung involviert.
EP12739639.8A 2011-01-28 2012-01-30 Formung eines ferromagnetischen metallglases durch schnelle kondensatorentladung Not-in-force EP2668307B1 (de)

Applications Claiming Priority (2)

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US201161437096P 2011-01-28 2011-01-28
PCT/US2012/023177 WO2012103552A2 (en) 2011-01-28 2012-01-30 Forming of ferromagnetic metallic glass by rapid capacitor discharge

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EP2668307A2 EP2668307A2 (de) 2013-12-04
EP2668307A4 EP2668307A4 (de) 2015-03-04
EP2668307B1 true EP2668307B1 (de) 2017-05-24

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EP (1) EP2668307B1 (de)
JP (1) JP5939522B2 (de)
KR (1) KR101524547B1 (de)
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MX (1) MX2013008740A (de)

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Publication number Priority date Publication date Assignee Title
US3332747A (en) * 1965-03-24 1967-07-25 Gen Electric Plural wedge-shaped graphite mold with heating electrodes
GB2148751B (en) * 1983-10-31 1987-01-21 Telcon Metals Ltd Manufacture of magnetic cores
JP3011904B2 (ja) * 1997-06-10 2000-02-21 明久 井上 金属ガラスの製造方法および装置
FR2806019B1 (fr) * 2000-03-10 2002-06-14 Inst Nat Polytech Grenoble Procede de moulage-formage d'au moins une piece en un verre metallique
CN1256460C (zh) * 2003-05-27 2006-05-17 中国科学院金属研究所 高热稳定性块体铁磁性金属玻璃及合成方法
US7732734B2 (en) * 2004-09-17 2010-06-08 Noble Advanced Technologies, Inc. Metal forming apparatus and process with resistance heating
KR101304049B1 (ko) * 2008-03-21 2013-09-04 캘리포니아 인스티튜트 오브 테크놀로지 급속 커패시터 방전에 의한 금속 유리의 성형

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BR112013018948A2 (pt) 2019-09-24
JP5939522B2 (ja) 2016-06-22
KR101524547B1 (ko) 2015-06-03
MX2013008740A (es) 2014-01-20
EP2668307A4 (de) 2015-03-04
EP2668307A2 (de) 2013-12-04
KR20130128454A (ko) 2013-11-26

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